Hydrocarbon Processing 03 2012

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HydrocarbonProcessing.com | MARCH 2013
CORROSION CONTROL
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MARCH 2013|Volume 92 Number 3
HydrocarbonProcessing.com
Cover Image: Catalytic reformer No. 3 at BPs Kwinana refinery, Western Australia.
SPECIAL REPORT: CORROSION CONTROL
35 Monitor and minimize corrosion in high-TAN crude processing
S. Ghoshal and V. Sainik
39 Mitigate reactor failures due to graphitization
A. Al-Meshari, A. Abdelgalil and S. Al-Enazi
43 Consider dewpoint corrosion in reactor design
K. Ramesh
51 Corrosion under insulation is a hidden problem
T. Hanratty
BONUS REPORT: SAFETY DEVELOPMENTS
55 Process safety management: Going beyond functional safety
M. A. Turk and A. Mishra
65 Operator response to alarms is an important protection layer
R. Limaye
71 Key aspects of design and operational safety
in offsite storage terminals
V. Ramnath, Aker Solutions, Pune, India
CATALYSTSUPPLEMENT
77 Optimize feed treatment for polypropylene process
H. Poorkar, H. Shbrain, S. Al-Harbi and A. Al-Saeed
78 Catalyst news
REFINING DEVELOPMENTS
95 Improve benzene control
L. McDermott and A. Malik
CLEAN FUELS
99 FCC catalyst design evolves to maximize propylene
C. Pouwels and K. Bruno
DEPARTMENTS
4 Industry Perspectives
8 Brief
11 Impact
15 Innovations
106 Marketplace
109 Advertiser index
COLUMNS
21 Reliability
How the best lubricant
provides added value
23 Integration Strategies
Wireless sensing benefits
from new technology
25 Boxscore Construction
Analysis
Saudi Arabias plan for
near-zero-sulfur fuels
31 Viewpoint
Refiners have a new
learning curve with shale oil
110 Engineering Case Histories
Case 71: Statistical visual
data can be useful
in troubleshootingPart 2
34
8
4MARCH 2013|HydrocarbonProcessing.com
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EU leans forward on clean-fuel strategies
In late January 2013, the European Commission (EC) an-
nounced ambitious measures to ensure the buildup and stan-
dardization of alternative fueling stations across Europe. Much
of the earlier EC policy initiatives addressed fuels and vehicles,
but offered little guidance on distribution.
Vicious cycle. In the press release, the EC noted that the im-
plementation of clean-fuel programs are hindered by three
primary barriers:
High cost of alternative-fuel vehicles
Low consumer acceptance of alternative-fuel vehicles
Lack of recharging and refueling stations.
Refueling stations are not constructed because there are not
enough vehicles. Vehicles are not sold at competitive prices
because demand is low. Consumers do not buy the alternative
vehicles because they are expensive and there are insufficient
fuel stations.
The EC is proposing a package of binding targets for Mem-
ber States requiring a minimum level of infrastructure to sup-
port clean fuels, along side with common European Union
(EU)-wide standards for distribution equipment.
Standardization efforts. The new measures seek to simplify
distribution issues for vehicles powered by electricity, hydrogen
and natural gas.
Electricity. Across the EU, electric charging points vary
greatly. Germany, France, The Netherlands, Spain and the
UK are making progress with electric-refuel stations. The EC
announced the Type 2 plug as the common standard for re-
charging electric vehicles. EU automobile makers have sought a
common plug to build alternative-fuel stations.
Hydrogen. A significant number of hydrogen fuel stations
are operating in Germany, Italy and Denmark, although not all
are publically accessible. Under the proposal, existing hydrogen-
fuel stations would form a network with common standards to
ensure fueling capabilities.
Natural gascompressed and liquefied. In the EU, over
one million vehicles, mostly passenger cars, are powered by
compressed natural gas (CNG) and represent only 0.5% of the
vehicle fleet. By 2020, the industry aims to increase the CNG ve-
hicle fleet to 10 million units. Such an aggressive target requires
publically accessible refueling stations. These stations must have
standardize equipment and be available EU-wide.
Further development of alternative-fuel vehicles will require
cooperation, standardization and investment. The EC estimates
that approximately 10 billion will be necessary to build the
minimum infrastructure for alternative fuels by 2020. The
proposal is based on the premise that the market will grow and
finance itself without the need to involve public funds.
An expanded version of Industry Perspectives can
be found online at HydrocarbonProcessing.com.
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Brief
Galveston Bay refinery
Marathon Petroleum has closed its transaction with BP to purchase
several assets, including the 451,000-bpd refinery located in Texas
City, Texas. The refinery will be renamed and referred to in future
Marathon communications as the Galveston Bay refinery. The deal
also includes a 1,040-megawatt cogeneration facility, four light
product terminals located in the US Southeast, retail marketing
contract assignments for approximately 1,200 branded sites
representing approximately 61,000 bpd of gasoline sales, three
operating intrastate natural gas liquids pipelines originating at
the refinery and a 50,000-bpd allocation of BPs Colonial Pipeline
shipper history. The base purchase price is approximately $598
million, plus inventories valued at approximately $1.1 billion.
Photo: Marathons Galveston Bay refinery in Texas City, Texas.
Hydrocarbon Processing|MARCH 2013 9
BILLY THINNES, TECHNICAL EDITOR / Billy.Thinnes@HydrocarbonProcessing.com
Brief
The Canadian National Energy Board has approved
an application by LNG Canada Development Inc. for a
license to export liquefied natural gas (LNG) from a proposed
terminal near Kitimat, British Columbia. The export license
will authorize LNG Canada to export 670 million tons of LNG
over a 25-year period. The maximum annual quantity allowed
for export will be 24 million tons of LNG. LNG Canada is a
consortium led by Royal Dutch Shell. Shells partners in the
project include PetroChina, Korea Gas and Japans Mitsubishi. As
part of the project, Shell plans to build a pipeline that will connect
gas fields in northern British Columbia to the Kitimat terminal.
Hess will pursue the sale of its terminal network in the
US and complete its exit from the refining business by
closing its refinery in Port Reading, New Jersey. The terminal
network is located along the US East Coast and has a total of
28 million barrels of storage capacity in 19 terminals, 12 of
which have deepwater access. The terminals previously served
as the primary outlet for Hess share of production from its
Hovensa joint venture refinery, most of which was used to
supply Hess retail and energy marketing businesses. With the
closure of the Hovensa refinery in 2012, as well as Hess ability
to access refined products from third parties to supply these
marketing businesses, the terminal system is no longer core to
the companys operations. The companys St. Lucia oil storage
terminal in the Caribbean, with 10 million barrels of capacity,
will also be included in the package for divestiture.
The Port Reading refinery is comprised solely of a fluid
catalytic cracking unit, and it primarily manufactures gasoline
and components used for blending heating oil. The refinery
incurred losses in two of the past three years. The financial
outlook for the facility is expected to remain challenged due to
the requirement for future expenditures to comply with envi-
ronmental regulations for low-sulfur heating oil and the weak
forecast for gasoline refining margins.
Hess has retained Goldman, Sachs & Co. as its financial advi-
sor for the divestiture of the terminal network.
Although overall output rose during 2012, Chinas
petrochemical industry witnessed a year-on-year fall in
profits on account of poor demand, according to a statement
from the countrys National Development and Reform
Commission. The Chinese petrochemical industry rose at a
12.9% rate year-on-year, growing to $1.73 trillion by the end
of 2012. Due to waning domestic and international demand,
the output continued to experience month-on-month declines
during the first six months of the year; however, it started
rebounding in the second half of the year on account of the
governments pro-growth policies, the statement said. These
policy implementations included reducing benchmark interest
rates, approving large-scale infrastructure projects and easing
the commercial banks reserve requirement ratio. Even with
those policies in place, the sectors profits dipped 9.4% from
JanuaryNovember 2012. According to Chinas National Bureau
of Statistics, the Chinese economy posted 7.8% growth during
2012, which is the lowest growth rate since 1999.
Mitsui Chemicals will withdraw from the business
operations of Keiyo Ethylene (KEC), a joint venture
with Maruzen Petrochemical and Sumitomo Chemical. Mitsui
Chemicals commenced equity participation (22.5%) in KEC in
December 1995 as part of an effort to reinforce Japanese olefin
supply infrastructures. However, recent changes in the global
ethylene market (such as the improvement in supplies from new,
large-scale plants in the Middle East and China and forecasted
production increases from shale gas in the US) have resulted
in a need to fundamentally restructure and reform Japans
petrochemical businesses for industry sustainability. An ethylene
production surplus is expected at facilities in the Ichihara (Chiba,
Japan) area, while domestic production is expected to fall below
6 million tpy. Mitsui Chemicals studied the value of continued
participation in KEC and decided it would be best to exit the
joint venture.
PetroChina and INEOS have completed a deal to
form joint ventures that include trading and refining
activities at the Grangemouth refinery in Scotland and the Lavra
refinery in France. The business employs approximately 1,000
people and has a turnover of $15 billion. PetroChina paid a little
over $1 billion cash for the shares in the joint ventures. Li Keqiang,
the Chinese vice premier, and Nick Clegg, the British deputy
prime minister, witnessed the signing of the framework agreement.
The joint ventures with INEOS are consistent with Petro-
Chinas strategy to build its broader business platform in Eu-
rope, said Si Bingjun, general manager of PetroChina Interna-
tional London.
OAO Novatek has signed a one-year agreement with
the Yeochun Naphtha Cracker Center (YNCC), a South
Korean petrochemical company, for the supply of up to
300,000 tons of light naphtha produced at the gas condensate
transshipment and fractionation complex in Ust-Luga,
Leningrad Oblast, Russia.
Novatek has already worked out reliable logistics of prod-
uct supplies to South Korea, and we are confident in the secu-
rity of supply of the required volumes of naphtha as a feedstock
for our production, said Paul Joo, the executive vice president
of YNCC.
The Ust-Luga complex includes facilities for transshipment
and fractionation of stable gas condensate. YNCC produces
ethylene, propylene, benzene, toluene and xylene, with prod-
uct output at three plants amounting to 4.3 million tpy.
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Impact
BILLY THINNES, TECHNICAL EDITOR / Billy.Thinnes@HydrocarbonProcessing.com
Chevron hit with hefty
penalties for Richmond
refinery fire
The California Division of the Oc-
cupational Safety and Health Adminis-
tration (Cal/OSHA) issued 25 citations
against Chevron USA, with proposed
penalties totaling nearly $1 million, for
state safety standard violations related
to the August 6, 2012 fire at Chevrons
Richmond refinery (FIG. 1). The citations
include 11 willful serious and 12 seri-
ous violations, resulting in the highest
penalties in Cal/OSHAs history.
On August 6, 2012, a fire broke out
at the refinery when a corroded pipe in
Chevrons No. 4 crude unit began leaking.
Cal/OSHA said in a statement, Chev-
ron managers did not shut down the unit
but instructed workers to remove insula-
tion, which led to the pipes rupture and
a massive fire. While there were no seri-
ous worker injuries, a reported 15,000
residents of surrounding communities
sought treatment after breathing emis-
sions from the fire.
Chevron responded to the citations
by reiterating its commitment to safe op-
erations. Although we acknowledge that
we failed to live up to our own expecta-
tions in this incident, we do not agree
with several of the Cal/OSHA findings
and its characterization of some of the al-
leged violations as willful, the company
said in a statement. Chevron plans to ap-
peal the judgment.
Cal/OSHA indicated that its inves-
tigation into the fire and the leak repair
procedures at the refinery revealed that
Chevron did not follow its own emergen-
cy shutdown procedures when the leak
was identified, and did not protect its
employees and employees of Brand Scaf-
folding who were working at the leak site.
Twenty-three violations were classi-
fied as serious due to the realistic possi-
bility of worker injuries and deaths in the
fire, Cal/OSHA said. Eleven of these seri-
ous violations were also classified as will-
ful because Cal/OSHA found Chevron
did not take reasonable actions to elimi-
nate refinery conditions that it knew
posed hazards to employees, and because
it intentionally and knowingly failed to
comply with state safety standards.
Cal/OSHA was also concerned that
there were violations in Chevrons overall
implementation of its own process safety
management (PSM) procedures. PSM
regulations require refineries to imple-
ment a comprehensive safety plan that
includes a precise determination of what
hazards exist and procedures to eliminate
or reduce them.
In an update to its own internal inves-
tigation, Chevron described the correc-
tive actions it has begun to develop and
implement. The company said that the
actions would strengthen process safety,
mechanical integrity and management
oversight. They included:
Enhancing inspections of piping
components potentially susceptible to
sulfidation corrosion, since carbon steel
components with low-silicon content
can corrode at an accelerated rate
Strengthening reliability programs
for piping and equipment, and enhancing
competency requirements for leaders, in-
spectors and engineers
Strengthening leak response proto-
cols and reinforcing wider authority to
shut down equipment
Creating more management over-
sight and accountability for process safe-
ty and re-emphasizing focus on process
safety.
Shale gas possible
catalyst for US
export growth
The American Chemistry Council
(ACC) recently released a report in which
it stated that the US chemical manufac-
turing sector is one of the most important
beneficiaries of the surplus of inexpen-
sive natural gas, helping to revive the US
manufacturing segment. This has also al-
lowed the US chemical sector to reassert a
strong position in global export markets.
FIG. 1. Chevrons refinery located in Richmond, California.
FIG. 2. US petrochemical plants, like the LyondellBasell polymers man-
ufacturing facility in Pasadena, Texas, are benefitting from abundant
supplies of shale gas.
Impact
12
According to the ACC, shale gas is a
critical component of a comprehensive
domestic energy plan that encourages the
development of the entire portfolio of
energy sources, including fossil fuels, re-
newables and energy efficiency. Access to
vast new supplies of domestic shale gas,
rich in the ethane needed for chemical
production, is revitalizing the US chemi-
cal industry (FIG. 2). The shale gas boom
has lowered input costs for the chemi-
cal sector, spurred demand for goods
derived from chemicals in international
markets and is driving a huge competi-
tive advantage for US producers. Exports
of US manufactured chemicals and plas-
tics have increased by 15% since 2010,
resulting in a record $34.7 billion trade
surplus. To continue serving interna-
tional and domestic markets, US chemi-
cal manufacturers have announced more
than $40 billion in new domestic capital
investments. Chevron Phillips Chemical
Co., ExxonMobil Chemical Co. and Dow
Chemical Co. are all building plants in
the US. Other North American produc-
ers are considering expanding or restart-
ing their existing facilities.
New production and associated activ-
ity is projected to accelerate economic
growth by 30 to 40 basis points. By 2020,
the cumulative impact could boost real
GDP by 2% to 3.3%. The ACC says in its
report that this could create the possibility
of 2.7 million to 3.6 million net new jobs.
The cost advantage resulting from lower
ethylene feedstock has put the US on an
entirely new path in cost competitiveness
while opening new export markets.
The ACC recommends that US policy-
makers refrain from taking action that
would distort the rapidly changing mar-
ket for natural gas. For instance, it said
that the US government should not act
to artificially inflate demand for natural
gas by subsidizing the purchase of natural
gas vehicles. Providing large government
incentives to stimulate one sector of the
natural gas market could put other sec-
tors at a competitive disadvantage, the
ACC said. The group also encouraged
Congress to:
Promote greater energy efficiency in
homes, buildings and industrial facilities
Apply economically competitive
approaches to encourage the adoption of
diverse energy sources, including energy
recovery from non-recycled materials and
other renewable sources
Adopt balanced regulatory policies
and permitting practices that will protect
the environment while allowing the US to
make the most of its vast resources
Avoid regulatory, tax or other poli-
cies that would increase the cost of contin-
ued development of domestic shale gas.
Biofuel mandate vacated;
agency responds by
increasing mandate 60%
In late January, the US Court of Ap-
peals for the DC Circuit vacated the
US Environmental Protection Agencys
(EPAs) 2012 cellulosic biofuel mandate,
concluding that its forecast was in excess
of the agencys statutory authority.
The courts decision provides wel-
come relief and puts the EPA on notice
that it must act as a neutral arbiter rather
than a promoter of cellulosic fuel, said
Analysis of Pressure Relief Devices
Contingencies analysis for emergency scenarios
Loads calculation by SS and Dyn Simulation
Relief devices (re-)sizing according to API Standard
PSV database creation/consolidation
Flare Header Design & Operational Analysis
Validation of existing flare header
Header hydraulics behavior
Temperature profiles
Dynamic analysis of peak loads simultaneity
Time duration of constraints violations
Flare Radiation Analysis
Multiple flare in multiple stacks
Shielding with water curtains or physical barriers
Sterile Area definition
Dynamic radiation and temperature prediction
Integrated Flare
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Reducing CapEx in revamp and expansion
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Impact
13
American Fuel and Petrochemical Manu-
facturers President Charles T. Drevna. In-
stead of facing the reality of zero cellulosic
biofuel production under the Renewable
Fuel Standards (RFS), the EPA wrongly
relied upon an inflated production capac-
ity predicted by cellulosic biofuel produc-
ers. This resulted in a cellulosic mandate
that was impossible to meet and left refin-
ers having to purchase waiver credits that
act as a hidden tax on transportation fuels.
While the court acknowledged that the
purpose of the RFS program was to in-
crease the production of clean renewable
fuels, it rejected the EPAs argument that
an aggressive cellulosic mandate was need-
ed to force new technology into the mar-
ketplace and held that refiners are in no
position to ensure, or even contribute to,
growth in the cellulosic biofuel industry.
An interesting development in this on-
going debate is the fact that only a week
after the Courts decision, the US EPA
rolled out its proposed 2013 percentage
standards for four fuel categories that are
part of the RFS. Surprisingly, these pro-
posed standards indicate that the US EPA
intends to increase the cellulosic ethanol
requirement by more than 60% from 2012
levels. The 2013 program proposes the
blending of more than 1.35 billion gallons
of renewable fuels over the amount man-
dated for 2012.
The Energy Independence and Se-
curity Act of 2007 (EISA) established
the RFS program and the annual renew-
able fuel volume targets, which steadily
increase to an overall level of 36 billion
gallons in 2022, the EPA said in a state-
ment. To achieve these volumes, the
EPA calculates a percentage-based stan-
dard for the following year. Based on the
standard, each refiner and importer de-
termines the minimum volume of renew-
able fuel that it must ensure is used in its
transportation fuel.
The proposed 2013 overall volumes
and standards are:
Biomass-based diesel (1.28 billion
gallons; 1.12%)
Advanced biofuels (2.75 billion gal-
lons; 1.60%)
Cellulosic biofuels (14 million gal-
lons; 0.008%)
Total renewable fuels (16.55 billion
gallons; 9.63%).
In other EPA news, the agency is
proposing a structured process for buy-
ers of renewable identification numbers
(RINs) to verify validity. Under the pro-
posal, RINs would be verified through a
new voluntary quality assurance program
that also includes alternative compliance
options, which leverage existing industry
practices and market forces. Quality as-
surance plans (QAPs) would provide a
recognized means for independent third
parties to audit the production of renew-
able fuel and to verify that RINs have
been validly generated.
For RINs that have been verified ac-
cording to an approved QAP, the program
would provide protection against liabil-
ity for civil violations resulting from the
transfer or use of invalidly generated RINs
under certain conditions. The rule would
also specify both the conditions under
which invalid RINs must be replaced with
valid RINs, and by whom. The proposed
rule allows verification of RINs to begin
this year.
VISCOSITY PROCESS ANALYZER VISC-4
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Direct measurement of kinematic viscosity
Temperature stability ( 0.02 K) as dened in standard ASTM D445
Minimized maintenance expenditure
ATEX and CSA C/US certied
VISC-4
for measurement of base/lube oils, bunker fuels, gasoils, and crude oils
Contact Glenn.Fannin@bartec-benke.de
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Select 153 at www.HydrocarbonProcessing.com/RS Select 155 at www.HydrocarbonProcessing.com/RS
Electronic marshalling eliminates the rework, the redesign and the headaches.
With DeltaV Electronic Marshalling, Emerson lets you make I/O changes where and when you need
them without costly engineering and schedule delays. Our new DeltaV CHARacterization Module
(CHARM) completely eliminates the cross-wiring from the marshalling panel to the I/O cardregardless of signal
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Innovations
ADRIENNE BLUME, PROCESS EDITOR
Adrienne.Blume@HydrocarbonProcessing.com
Coating system gets
European patent
Hempels Ultra-High Solids and
Speed (UHSS), a two-coat protective
paint system certified for C5-M and
C4 corrosive environments, has been
granted a patent from the European Pat-
ent Office. The system is suitable for
paint shop application of steel parts for
refineries, the chemical industry, power
generation, infrastructure projects and
wind turbines.
Unlike standard systems, which use
three coats, UHSS uses just two high-
solids coatings to deliver a primer and
galvanic and UV protection. As a result,
UHSS can reduce volatile organic com-
pound emissions by up to 70% compared
to standard three-coat systems, depend-
ing on the system. It also dries six times
faster than standard three-coat systems,
helping increase production speeds. The
UHSS system is available globally.
Virtual engineer service
offers low-cost support
Rockwell Automations Virtual Sup-
port Engineer service allows original
equipment manufacturers (OEMs) to
offer highly secure, remote monitoring
and troubleshooting to their customers
without investing in expensive infra-
structure. This scalable, secure and cost-
effective remote monitoring solution
provides IT-friendly access that allows
OEMs to identify and resolve technical
issues, perform scheduled and preven-
tive maintenance, and monitor their in-
stalled machinery base to help optimize
machine performance.
While most other user solutions on
the market transfer data bidirectionally
through a firewall, the Virtual Support
Engineer service relies exclusively on
IT-approved outbound communication.
This helps prevent computer viruses,
worms and other digital threats tied to
inbound data transfer. Security is further
enhanced with recorded logins, audit
trails, video recording and optional ac-
cess on demand.
OEMs using the service receive ac-
cess to real-time alarm capabilities that
can be delivered via text message or
email to themselves, to their customers
or to a Rockwell Automation remote-
support application engineer. Alarm ca-
pabilities can also indicate the potential
for future equipment failures, allowing
OEMs to make proactive adjustments
prior to catastrophic failure.
In emergency situations, the Virtual
Support Engineer service proactively no-
tifies OEMs when equipment goes down.
Often, remote troubleshooting and on-
line adjustments made through the sys-
tem can remedy issues, therefore reducing
travel time and costs for OEMs and mini-
mizing downtime for their customers.
Pemex approves
composite systems
HJ3s CarbonSeal Industrial Com-
posite Systems have been qualified and
approved by Mexican state oil company
Pemex for the repair and strengthening of
low-risk and high-risk corroded or dam-
aged steel pipes. The approval covers
pipelines throughout Pemexs oil and gas
production process areas, including all
onshore, offshore, exploration, refining,
transmission and distribution pipelines.
HJ3 noted that the qualification opens
the door for its products to the Latin
American petrochemical and gas markets.
The qualifying process, which was
conducted by Instituto Mexicano Del
Petrleo (IMP), involved a series of in-
dividual strength and durability tests per
ASME PCC-2 Article 4.1 APPENDIX
3 ISO/TS-24817, Standards for the Re-
pair of Pressure Equipment and Piping.
Part of the test protocol included a burst
test to determine the ability of the Car-
bonSeal system to withstand internal
pressures over 5,000 psi when wrapped
over defects to include 80%90% steel
wall loss (FIG. 1).
Oil-mist system replaces
grease lubrication
Total Lubrication Management Co.
recently introduced the MistLock bear-
ing and motor (FIG. 2) for air-cooled heat
exchangers with oil-mist lubrication.
The technology allows the same oil-mist
system serving pumps and motors at
ground level to serve the fan air-cooler
bearings and motors that are tradition-
ally grease-lubricated.
The MistLock bearing and motor de-
sign for air coolers directs oil mist through
equipment bearings from top to bottom,
which is the most desired path for lubrica-
tion with oil mist. Drain connections are
provided to vent stray mist and coalesced
oil away from equipment, while allow-
FIG. 1. This CarbonSeal system withstood
a burst test wherein the steel pipe ruptured
at 5,200 psi.
FIG. 2. MistLock allows oil-mist systems to
serve both ground-level equipment and
equipment traditionally lubricated by grease.
Innovations
ing both to be recaptured in the patented
closed-loop oil-mist system design.
Optional mounting arrangements are
available on both the bearing and the mo-
tor to accommodate retrofits into new and
existing structures. Proprietary sealing
provides extended life while containing
the oil mist to prevent fouling of the cool-
ing coils. Extensive testing of the bearings
and motors with these seals has been per-
formed on test stands under extreme con-
ditions and on equipment under real-time
service conditions in refineries.
MistLocks bearing cartridge design
allows for both axial and nonparallel
misalignment, regardless of shaft orien-
tation. The cartridge design accommo-
dates up to a 20 misalignment between
the upper and lower bearing, eliminating
the need to shim bearings during installa-
tion. Special features in the upper bearing
allow for axial thermal expansion of the
fan shaft to prevent bearing overload.
The motor may be mounted vertically
in the shaft up or down positions, as
well as in horizontal positions, to allow
for use on right-angle gear-drive fan ap-
plications. The motor comes in a wide
range of sizes that fit most air-cooler ap-
plications. Additionally, the epoxy coat-
ing on the motor windings and the lead
wire insulation have been tested to ensure
that degradation and oil wicking will not
occur from the use of modern synthetic
oils used in many oil-mist systems.
Portable chromatograph
measures gas Btu
AMETEK Process Instruments Chan-
dler Engineering Model 292B portable
gas chromatograph (FIG. 3) determines
the energy content (Btu) of natural gas.
The chromatograph features a fully inte-
grated sample handling system, rugged
chromatograph module, and enhanced
data-processing and data-handling capa-
bilities, including an LCD color display
and user interface.
Sample transport, signal integration
and system diagnostics are handled within
the unit to ensure accurate, reliable and
repeatable analysis. The units advanced
electronics platform accurately deter-
mines energy content, relative density and
compressibility based on industry-stan-
dard calculation methods.
Integrated optimization functions re-
sult in exceptional sensitivity and peak per-
formance. An integrated sample inlet man-
ifold allows for single-point connections of
sample and drive (carrier) gases, permit-
ting installation either as a standalone ana-
lyzer or integrated into a mobile platform
such as a truck, van or other vehicle.
Sample results, including live chro-
matograms, raw data information, analy-
sis reports and calibration data can be
easily viewed on the front-panel LCD
display. System and analysis reports can
be retrieved via a USB port, customized
to meet user requirements, and printed
directly from the unit. The Model 292Bs
advanced software and two onboard
computers allow the unit to calculate
heating value, relative density and com-
pressibility using the AGA-8 method.
X-ray analyzer enables
fast, precise detection
Thermo Fisher Scientific Inc. has re-
leased a 200-watt version of its Thermo
Scientific ARL OPTIMX Wavelength
dispersive X-ray fluorescence (WDXRF)
analyzer (FIG. 4). The ARL OPTIMX Se-
ries uses WDXRF analysis techniques to
assist in determining the elemental com-
position of a wide range of samples, both
solids and liquids, at a high resolution.
The analyzer enables lower limits of
detection, two to three times faster analy-
sis and higher sample throughput. The in-
strument features SmartGonio, an inno-
vative goniometer that can be configured
to cover all elements, from fluorine to
uranium, in sequential mode. For critical
elements, two fixed channels can be fitted
alongside the SmartGonio to reduce total
analysis time and improve performance.
The ARL OPTIMX Series also fea-
tures Ultra Closely Coupled Optics tech-
nology, which is designed to enable the
instruments to perform at levels as high
as three times their nominal power. Tem-
perature regulation of both the spectrom-
eter and the crystals improves stability
and repeatability, complying with ASTM
and ISO regulations. The compact instru-
ments offer consistent performance with-
out the need for water cooling.
Monitor detects hazardous
gases in workplace
The Drger X-am 5100 monitor de-
tects hydrogen fluoride (HF), hydro-
gen chloride (HCI), hydrogen peroxide
(H
2
O
2
) and hydrazine (N
2
H
4
) reactive
gases. The portable monitor is well suited
to applications such as monitoring alkyla-
tion units in the petrochemical industry,
checking HF during the injection process
for the extraction of crude oil, monitor-
ing hydrazine used for propulsion, and
other uses.
The special design of the monitor pre-
vents reactive gases from depositing on the
housing (i.e., gas adsorption). Direct gas
entry to the sensor, fast sensor response
times and precise measurement results are
also ensured with this design. If the moni-
tors alarms are activated, it warns the user
with audible, visual and vibration alarms.
The monitor is protected against dust
and water ingress. It also features explo-
sion protection and is resistant to high
FIG. 3. The Model 292B portable gas
chromatograph analyzes the energy content
and composition of natural gas.
FIG. 4. The 200-watt ARL OPTIMX analyzer
uses wavelength dispersive X-ray fluorescence
analysis techniques to determine elemental
composition of samples.
Innovations
17
impacts and vibrations. Electromagnetic
compatibility has also been tested. Ad-
ditionally, the monitors intuitive menu
is easy to navigate with just two buttons.
First SO
2
-/CO
2
-capture
plant begins operation
In capturing the first carbon diox-
ide (CO
2
) at their joint demonstration
plant at the Aberthaw power station in
the UK, Cansolv and RWE npower have
successfully commenced operations at
the worlds first integrated sulfur dioxide
(SO
2
-)/CO
2
-capture plant. The post-
combustion plant will capture 50 metric
tons of CO
2
per day from Aberthaws
flue gases, using Cansolvs SO
2
and CO
2
scrubbing technologies.
The announcement highlights the suc-
cessful commissioning of this regenerable
carbon-capture testing campaign, which
will see 90% of CO
2
captured and essen-
tially all SO
2
captured. The use of a regen-
erable technology can also avoid landfill
produced from conventional non-regen-
erable systems in reusing the absorbent.
This is achieved by continuous recycling;
the result is less waste and cost savings
without the need to restock.
Cansolv and RWE npower plan to
initiate a research and development pro-
gram focused on further optimization
of the process and demonstrating the
advantages of new-generation solvents.
The environmental performance of the
process will also be assessed during the
pilot phase, at which time Cansolv and
RWE npower will be working with the
UK Environment Agency to track and
evaluate the environmental aspects of
CO
2
-capture technology for coal-fired
power stations.
Ring system protects
storage tanks
MATCORs turnkey cathodic protec-
tion solutions are available to a variety of
leading liquid terminal operators. These
storage facilities hold and distribute crude
oil, refined products and specialty liquids.
MATCOR solutions protect aboveground
storage tank units within these terminals,
using a proprietary concentric ring system.
MATCORs turnkey solution involves
several areas of the business.The company
provides a wide range of services that in-
clude design and engineering of custom
cathodic protection solutions for new and
existing ASTs; custom manufacturing of
SPL mixed metal oxide anodes; instal-
lation and site management; and single-
point-of-contact project management
that follows an established project meth-
odology to offer a consistent approach
for each engagement. Additionally, MAT-
COR provides continued services to the
client with monthly and annual surveys at
other terminal locations.
MATCORs unique capability as a
full-service provider demonstrates that,
regardless of the size of the storage tank
or the location, MATCOR has the re-
sources to provide a turnkey cathodic
protection solution specifically designed
to meet the clients unique needs. Exam-
ple specifications for solutions are:
Customized, concentric-ring-impressed
systems for external tank bottoms:
30-year design life standard; 50-
year (or longer) design life available
Factory assembled; no cutting,
splicing or welding required in the field
Easy to install; less than four hours
for an 80-m (250-ft) diameter tank
Mixed metal oxide with coke back-
fill to minimize oxygen (depolarizer)
generation.
Internal tank CP systems:
30-year design life
Vertical and horizontal configura-
tions available
Utilizes MMO wire anodes with ex-
terior braiding
Available in platinum for potable
water applications
Factory assembled; no cutting,
splicing or welding required in the field.
FIG. 5. MATCOR solutions protect
aboveground storage tanks, using a
proprietary concentric ring system.
Advanced Inspection and Assessment Solutions
for Process Fired Heater Coils
Learn more about FTIS through animation on our website:
www.QuestIntegrity.com/FTIS
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NEW DELHI, INDIA | 911 JULY
2013 IRPC Advisory Board Members:
ANDREA AMOROSO
Vice President, Process Technology
eni - Rening & Marketing Division
A. K. ARORA
Director General
Petroleum Federation of India
JOHN BARIC
Licensing Technology Manager
Shell Global Solutions International B.V.
ANINDYA SUNDAR BASU
Managing Director
Chennai Petroleum Corporation Ltd
ERIC BENAZZI
Marketing Director
Axens
CARLOS CABRERA
Executive Chairman
Ivanhoe Energy
DR. CHARLES CAMERON
Head of Technology, Downstream;
VP, Formulated Products Technology
BP plc
GIACOMO FOSSATARO
General Manager
Walter Tosto S.p.A.
DR. MADHUKAR ONKARNATH GARG
Director
CSIR-Indian Institute of Petroleum
RAJKUMAR GHOSH
Director (Reneries)
Indian Oil Corporation Limited (Reneries Division)
CHAKRAPANY MANOHARAN
Director-Renery
Essar Oil Ltd.
B. K. NAMDEO
Executive Director,
International Trade & Supplies
Hindustan Petroleum Corporation Limited
SYAMAL PODDAR
President
Poddar & Associates
A.K. PURWAHA
Chairman & Managing Director
Engineers India Limited
GIACOMO RISPOLI
Executive Vice President,
Research & Development and Projects
eni - Rening & Marketing Division
STEPHANY ROMANOW
Editor
Hydrocarbon Processing
DR. AJIT SAPRE
Group President
Research and Technology
Reliance Technology Group
MICHAEL STOCKLE
C Eng FlChemE
Chief Engineer - Rening Technology
Foster Wheeler
K VENKATRAMAN
Chief Executive Ofcer
& Managing Director
Larsen & Toubro
S VENKATRAMAN
Director (Business Development)
Gail (India) Limited
HPIRPC.com
Hydrocarbon Processing is bringing its market-leading rening
and petrochemicals conference to New Delhi in 2013
For the past three years, executives and technical professionals in the global rening and petrochemical industry have gathered
at Hydrocarbon Processings International Rening and Petrochemical Conference (IRPC) to explore the latest advancements
in technology and operations. Now in its fourth year, the conference will be held 911 July 2013 in New Delhi, India. This is a
one-of-a-kind, interactive opportunity for hydrocarbon processing industry (HPI) professionals to network and share the kind
of knowledge that has a direct and meaningful impact on the strategies and plans for those involved.
With the HPI evolving to meet new challenges and capitalize on new opportunities, managers and engineers are actively
seeking information and solutions to make their companies more efcient and protable.
This is your chance to take part in the discussion and be among your peers and other industry innovators to discuss how
the latest technology and trends can be applied at reneries and plants. Key topics to be covered are: plant and renery
sustainability, energy policy, clean fuels, gas treatment, rotating equipment, rening and petrochemical integration, maintenance
and reliability, and more. View the conference agenda online at HPIRPC.com.
Global HPI: In India, growth brings opportunities for the application of new
technology and learning
As one of the fastest growing centers of energy consumption and production, India is an ideal place for global industry
leaders to gather during IRPC 2013. One of the developing economies driving new demand for transportation fuels, India has
an expanding GDP and large population, and its demand for all energy forms continually increases. As of 2012, India has 20
major reneries in operation with a combined capacity of 187.4 MMtpy. Looking forward, companies like Indian Oil Corporation
Limited will continue to increase rening capacity as demand for domestic vehicles and transportation fuels increases.
Why attend IRPC 2013?
Join international HPI professionals from around the world, representing operators, reneries and petrochemical plants
like Abu Dhabi Gas Industries, BP plc, Chevron Lummus Global LLP, ConocoPhillips Ltd, eni, ExxonMobil Research &
Engineering Company, Indian Oil Corporation, Linde Gas, Lukoil, PDVSA and Total
Ample networking opportunities between sessions allowing you to connect with old and new business contacts
Explore and learn more about the latest developments within the HPI
Get local and global perspectives on the HPI, rening and petrochemicals
Register Early and Save!
Take advantage of our Early Bird discount when you register to attend by 29 March 2013. Bring a team of two or ve and save
even more. To reserve your spot at the conference, register online at HPIRPC.com or call +1 (713) 520-4402.
Conference venue: Taj Palace Hotel | Sardar Patel Marg, Diplomatic Enclave | New Delhi 110021 | India
Testimonials from past IRPC delegates:
It was really a nice experience, particularly from an information-sharing point of view and global cooperation.
Deputy General Manager, India
The exhibition was a great framework, and there was plenty of time to meet people and discuss.
R&D Project Manager, France
Conference Delegate Bag Sponsor: Technical Program Sponsor: Supported by: Rening Track Sponsor:
Conference Lanyard Sponsor: Program Print Sponsor: Speaker Gift Sponsor:
EVENT
Conference Host:
Hydro, Inc. l HydroAire, Inc. l Hydro East, Inc. l Evans Hydro, Inc. l Hydro South, Inc. l HydroTex Golden Triangle l HydroTex Dynamics, Inc.
HydroTex Deer Park, Inc. l CW Hydro, Inc. l Hydro Australia, Pty. Ltd. l Hydro Vietnam, Co. Ltd. l Safe-T Hydro, Inc.
Hydro Scotford, Inc. l Hydro Middle East, Inc.
Reliability
HEINZ P. BLOCH, RELIABILITY/EQUIPMENT EDITOR
Heinz.Bloch@HydrocarbonProcessing.com
How the best lubricant provides added value
In November 2012, a highly competent lubrication engi-
neer and I met again at the ExxonMobil Maintenance and Pro-
ductivity Improvement Symposium in San Antonio, Texas. We
talked about the small, but pesky, problems that we encounter
in our professional careers as engineers. In addition, we shared
our enthusiasm for understanding industrial lubrication, which
is a fascinating and evolving business.
New advanced products. We discussed a new advanced
lubrication product, the Mobil DTE 10 Excel 68. As shown
in FIG. 1, Mobil DTE 10 Excel 68 could be a possible sub-
stitute for the old Exxon Synesstic 100 in mist systems that
were commissioned in the late 1970s and early 1980s. We
agreed that reliability professionals must recall the rationale
used years ago to justify and explain lube issues. Since then,
with decades of advancements in lube formulation, we must
rethink and make adjustments to lubrication systems that in-
clude these new developments.
Case. For example, consider the viscosity vs. temperature
charts between the present Mobil DTE 10 Excel line and the
more expensive ISO VG100 diester lubricants used in the
1980s. Because the lubricants respective viscosities are similar
at elevated temperatures, and the DTEs pour point and cloud
point are sufficiently low, the modern DTE 10 Excel 68 will
work very well in the coldest temperatures that South Texas fa-
cilities experience. The change could also save energy.
The DTE contains no zinc (Zn). Under certain conditions,
Zn can degrade and form sludge. Some VG100 and VG150 pre-
cursor formulations have served well in the past. However, with
new information, these lubricant oils may represent overkill
in oil-mist systems used along the US Gulf Coast. Moreover,
these lubricants are unsuitable for high-speed equipment with
oil rings (slinger rings).
1
Another issue. Our discussion revisited old arguments regard-
ing operating A process pumps and how frequently to switch
over to the B set. The author still believes that best-practice
plants applying pure oil-mist systems should alternate between
A and B pumps every four to six weeks. Plants with process
pumps using conventional oil-sump lubrication must visualize
that the ball separators (cages) rotate a half turn per full turn of
a shaft. Therefore, they should manually and periodically rotate
the B shaft three or four turns; such actions would be needed
to wet all bearing components. Manual rotation would ensure
that all surfaces are coated. The procedure would prevent bear-
ing elements from sitting in the same spot. Also, rotation de-
creases the risk of bearing damage due to vibration transmitted
from an adjacent operating machine.
Still, adopting a monthly alternate running routine would
be more beneficial than manual rotation. Running will drive off
some moisture from the old-style bearing housings. There are
concerns with open-breather vents that allow atmospheric dust
and water vapor to wreak havoc on oil. Starting vented-housing
pumps will also stir up sludge. Even worse is the practice of on-
off bumping the pump with an electric motor. Most wear on
bearings and oil slinger rings occurs at startup. Frequent starts
of semi-dry bearings can do more harm than false brinelling.
Bottom-line issues. Plant engineers should use lube-applica-
tion engineers as resources in bearing, fluid sealing and bearing
protector seal applications. Even the best lubricants will suffer if
seal components degrade and contaminate the oil. Quality and
long-term reliability are not cheap. The gleam of lowest-cost
oil quickly dissipates with the repair costs and lost profit due to
equipment unavailability.
LITERATURE CITED
1
Bloch, H. P., Pump Wisdom: Problem Solving for Operators and Specialists,
John Wiley & Sons, Hoboken, New Jersey, 2011.
43C
55C
66C
77C
88C
97C
107C
43C
-60
-50
-40
-30
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
55C
66C
77C
88C
97C
107C
92C 978C 103C 108C 114C 114C 118C
Efective temperature
T
e
m
p
e
r
a
t
u
r
e
,

C
ISO 15
ISO 22
ISO 32
ISO 46
ISO 68
ISO 100
ISO 150
Minimum viscosity 13 cSt after shear
Viscosity 860 cSt load
Maximum viscosity 9,300 cSt no load
FIG. 1. Temperature operating windows for an entire industrial
lubricant series. Source: ExxonMobil Lube Marketing Literature.
HEINZ P. BLOCH resides in Westminster, Colorado.
His professional career commenced in 1962 and included
long-term assignments as Exxon Chemicals regional
machinery specialist for the United States. He has
authored over 520 publications, among them 18
comprehensive books on practical machinery
management, failure analysis, failure avoidance,
compressors, steam turbines, pumps, oil-mist lubrication,
and practical lubrication for industry. Mr. Bloch holds
BS and MS degrees in mechanical engineering. He is
an ASME Life Fellow and maintains registration as
a Professional Engineer in New Jersey and Texas.
Treating of Jet Fuels at a
Lower Cost
Patented FIBER FILM technology and a proprietary treating solution sweeten
mercaptans without the need for a solid bed media. The result is lower capital and
operating costs, a higher on-stream factor, and a smaller plant footprint.
www.merichem.com
Sweet Solutions.
MERICAT J
Integration
Strategies
HARRY FORBES, CONTRIBUTING EDITOR
Hforbes@ARCweb.com
Wireless sensing benefits from new technology
Wireless sensing is the most important new technology to
emerge in decades for process measurement and equipment
monitoring applications. For this reason alone, it has attracted
the sustained attention of ARC Advisory Group and other in-
dustry analyst organizations. While growth of wireless mea-
surements in industrial applications has proven to be slower
than most forecasts, wireless continues to grow at a much faster
rate than the overall automation market.
Looking at the changes in wireless sensor networking
(WSN) last year, ARC is most impressed by the greater ma-
turity of the industry, along with significant new technical
achievements. We believe that both will spur market growth
because they enable a much larger set of customers to be well
served. Recent events help illustrate how these developments
have changed (and will continue to change) the wireless sens-
ing market.
Commercial maturity. Greater WSN industry maturity has
come through a steady series of acquisitions. At present, almost
all of the pioneering sensor-networking ventures have been ac-
quired by much larger companies. Most of the acquirers are
well-established semiconductor suppliers. Virtually all of the
fabless WSN firms have now been snapped up. Dust Networks
has become one of the most recent, acquired in late 2011 by
specialist Linear Technology Corp.
Fortune 1000 companies must carefully manage the tech-
nologies they apply if they are to meet their customer ex-
pectations. A technology that is sourced from a group of
venture-stage fabless semiconductor firms represents a ma-
jor supply-chain risk to global firms whose customers expect
product support for many years going forward. Today, the list
of WSN suppliers no longer represents an exceptional risk to
the supply chains of global giants like Emerson, GE, Honey-
well and Siemens.
Technical growth. WSN has also grown technically dur-
ing the past year. The most important development is the
completion of the e revision to the IEEE 802.15.4 Standard.
Although the 15.4 Standard has been published for years, the
most commercial WSN applications have used nonstandard
medium access (MAC) rules to optimize performance of their
own networks. WirelessHART, ISA100.11a, ZigBee and IPv6
sensor networks all depended on a customized MAC layer to
achieve low power consumption and reliable end-to-end mes-
sage delivery. This limits the value of the IEEE standard, be-
cause applications needed their own specialized MACs.
IEEE 802.15.4e makes important changes to the defined
MAC layer. It creates a standard and fully defined MAC that
can support diverse network types. This includes 6LoWPAN-
compressed IPv6 networks. It also supports the synchronized
TDMA network properties used in industrial low-power ap-
plications, e.g., WirelessHART and ISA100.11a. Finally, 15.4e
accommodates extensions, so that these diverse networks (as
well as future ones) can extend the standard MAC without vio-
lating the standard itself. This decouples WSN development
from the three- to four-year-long IEEE standards development
process. It will give the IEEE standard greater value and a much
longer life, enable greater interoperability among WSN silicon
and network stacks, and enable future WSN technologies to
leverage an existing, fully standard MAC.
Contributors. The new standard was developed largely from
Dust Networks technology, with extensive and enthusiastic
contributions from many major suppliers, notably including
Siemens.
Dust Networks now uses its most recent chip design (which
conforms to 15.4e) in both WirelessHART and IPv6 products.
Using the latest chipset is a large benefit for the WirelessHART
(industrial) customers, since it helps to reduce power con-
sumption by roughly 50% with each new generation.
In battery-powered industrial devices, this provides an en-
ergy surplus, thus enabling devices to have longer service life
and/or to serve in applications that previously consumed too
much battery power.
IPv6 applications can use a wider variety of system architec-
tures. In particular, they can route packets from field sensors to
analytics and applications that are truly location-independent,
including cloud-based applications. It remains to be seen what
impact the cloud will have on the wireless sensing market, but
the combination of high scalability and low cost offered by
cloud services may enable new applications that are not fea-
sible when built using traditional WSN gateways.
Energy harvesting. Another area to watch may be energy
harvesting. Although energy harvesting represents an ongoing
technical challenge, it is a very active development area at sev-
eral specialist companies. Low-power products will be the first
to benefit from any new harvesting solutions that emerge.
HARRY FORBES is a senior analyst at ARC Advisory
Group. His research focuses on the impact of industrial
networking and wireless technologies on todays
manufacturing. He also covers smart grid and the
electric power vertical industry. His research topics
include the smart-grid, smart-metering and smart-
energy technologies. Mr. Forbes is a graduate of Tufts
University with a BS in electrical engineering and has
an MBA from the Ross School of Business at the
University of Michigan.
Boxscore Construction
Analysis
LEE NICHOLS, DIRECTOR, DATA DIVISION
Lee.Nichols@GulfPub.com
Saudi Arabias plan for near-zero-sulfur fuels
Around the world, legislation mandat-
ing decreased emissions and lower levels
of airborne pollutants is coming into ef-
fect. In response, refiners are implement-
ing operational and processing changes to
reduce sulfur levels in transportation fuels.
To comply with mandatory sulfur
specifications for gasoline and diesel be-
tween 2013 and 2016, the Kingdom of
Saudi Arabia plans to spend billions of
dollars to construct multiple clean-fuel
projects. Saudi Arabia has adopted Euro-
pean standards for fuel quality, as Europe
has been the frontrunner on regulations
for low-sulfur, clean transportation fuels.
Clean-fuel goals. Saudi Arabia is seek-
ing to reduce sulfur content in diesel and
gasoline to 10 parts per million (ppm)
and to lower benzene content in gasoline
to 1%. With these new fuel specifica-
tions, Saudi Arabian refining operations
will comply with international standards.
This will represent a dramatic reduction
in sulfur levels from June 2012, when
Saudi Arabias maximum sulfur level for
diesel was greater than 500 ppm (FIG. 1).
The planned upgrades and revamps are
necessary to meet future market demand
for higher-value, lower-sulfur transporta-
tion fuels.
Along with its joint ventures (JVs),
Saudi Arabian national oil company Sau-
di Aramco will upgrade all of the King-
doms domestic refineries to produce
lower-sulfur transportation fuels. Sev-
eral projectsthe Ras Tanura Refinery
Clean Fuels and Aromatics project, the
Riyadh Refinery Clean Transportation
Fuel project, the Saudi Aramco Mobil
Refinery Co. (SAMREF) Clean Fuels
project and the PetroRabigh Clean Fuels
projectare designed to accomplish the
kingdoms goal of producing near-zero-
sulfur fuels by 2016.
Ras Tanura Refinery Clean Fuel and
Aromatics project. The Ras Tanura re-
finery is Saudi Aramcos most complex
refinery. Located on the Arabian Gulf,
Ras Tanura has a crude distillation ca-
pacity of 550 thousand barrels per day
(Mbpd), a 305-Mbpd natural gas liquids
(NGLs) processing facility, a 960-Mbpd
crude oil stabilization facility and 75
crude oil storage tanks with a combined
capacity of 5.8 million barrels (MMbbl).
Most of Ras Tanuras production is slated
for domestic use.
The $3 billion (B) project is sched-
uled for completion in 2016. The projects
main goals are to produce cleaner fuels
and to increase production of paraxylene,
benzene and toluene. Annual production
capacity could reach 1 million tons per
year (MMtpy) of aromatics.
In May 2011, Jacobs Engineerings
Middle Eastern unit, Jacobs, Zumal and
Turbag Consulting Engineers (Jacobs
ZATE) was awarded the front-end en-
gineering and design (FEED) contract
under Saudi Aramcos General Engineer-
ing and Project Management Services
(GES+) contract. Jacobs acquired ZATE
in 2008 to fulfill Saudi Aramcos GES+ ini-
tiative. The GES+ initiative is designed to
increase local content in Saudi Arabia for
engineering services such as FEED, fea-
sibility studies, procurement and project
management services.
Jacobs will be responsible for FEED
services for both inside and outside bat-
tery limits. These services include modi-
fications to the refinery to comply with
future environmental regulations and to
increase diversity of petrochemical prod-
ucts. FEED should be completed in early
2013, with calls to tender for multiple en-
gineering, procurement and construction
(EPC) contracts scheduled for the second
quarter of 2013.
Riyadh Refinery Clean Transportation
Fuel project. Located in the central region
of Saudi Arabia, the 124-Mbpd Riyadh re-
finery is supplied with crude oil from the
East-West pipeline. In April 2011, Foster
Wheeler and A. Al-Saihati, A. Fattani & O.
Al-Othman Consulting Engineering Co.
(SOFCON) were awarded the FEED and
project management consultancy (PMC)
services contracts for this project.
The $1 B upgrade project is designed
to reduce sulfur content in diesel from
330 ppm to 10 ppm and to also decrease
benzene levels in gasoline. It is the first
brownfield project of this magnitude to
be awarded by Saudi Aramco. The project
scope includes:
Four new processing unitsisom-
erization, naphtha splitting, sulfur guard-
Source: United Nations Environmental Programme (UNEP)
> 5,001 and above
Conicting/missing data
15 and below
> 1650
> 51500
> 5012,000
> 2,0015,000
FIG. 1. Global status of maximum allowable sulfur in diesel fuel, parts per million (June 2012).
Boxscore Construction Analysis
bed and diesel hydrotreating
Two debottlenecking operations on
the hydrocracker and gas concentration
units
Replacement of the crude and vacu-
um distillation tower internals.
Submission of bids for the EPC con-
tract ended in October 2012. Saudi Ar-
amco expects to award the EPC contract
in early 2013 to Daelim Industrial, JGC
Corp., Saipem or Samsung Engineering.
SAMREF Clean Fuels project. SAM-
REF is an equally owned JV between
Saudi Aramco and ExxonMobils wholly
owned subsidiary, Mobil Yanbu Refining
Co. Located on the coast of the Red Sea,
SAMREFs Yanbu refinery is the worlds
largest single-train refinery. This site pro-
cesses 400 Mbpd of crude oil into fuels,
of which half is consumed domestically.
SAMREFs Yanbu refinery will under-
go significant modifications to produce
cleaner fuels by reducing sulfur levels by
more than 98% in gasoline by 2013, and in
diesel by 2016. The execution will be split
into two phases. Phase 1 will begin during
a 45-day maintenance shutdown in March
2013. A grassroots desulfurization train to
treat 60 Mbpd of fluid catalytic cracking
(FCC) gasoline will be installed. A revamp
of the 98-Mbpd distillate hydrotreater and
refinery utilities infrastructure will also
begin. WorleyParsons is responsible for
FEED and EPC of the facilities.
Phase 2 is scheduled to start up by the
end of 2015. The scope includes a new
high-pressure distillate hydrotreater, a
hydrogen manufacturing unit, a sulfur re-
covery unit, and offsites and utilities infra-
structure. The $2.5 B project is scheduled
for completion in 2016.
PetroRabigh Clean Fuels project.
Rabigh Refining and Petrochemical Co.,
or PetroRabigh, is an equally owned JV
between Saudi Aramco and Sumitomo
Chemical Co. of Japan. Located on Sau-
di Arabias west coast, the PetroRabigh
complex is one of the largest integrated
refining and petrochemical complexes in
the world. With a capacity of 400 Mbpd,
it is also designed to produce a total of 2.4
MMt of petrochemical solids and liquids.
To meet international environmental
standards, the $1 B clean-fuels project is
designed to reduce sulfur content in gaso-
line from 300 ppm to 10 ppm. At pres-
ent, the FEED contract is in the bidding
phase, with seven companies vying for the
contract. The scope of the FEED contract
includes designing the facilities, setting
specifications for equipment required,
evaluating potential licensors, adjusting
capital expenditures and operating costs,
and estimating labor and time frames for
the EPC phase.
Other projects. Saudi Arabia is not the
only Middle Eastern country with clean-fu-
els projects. Kuwaits national oil company,
Kuwait National Petroleum Co. (KNPC),
is investing $31 B in a project to modern-
ize the countrys Mina Abdullah and Mina
Al-Ahmadi refineries, as well as to increase
total crude oil throughput to 800 Mbpd.
KNPC will construct and revamp sev-
eral units in both refineries to process en-
vironmentally friendly fuels with signifi-
cantly lower sulfur content. Major units
to be added include atmospheric residue
GE
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The Emerson logo is a trademark and service mark of Emerson Electric Co. 2013 Fisher Controls International LLC. D352200X012 MZ8
Manually inputting
the control signal feels pretty primitive.
I need to get back in automatic mode
for better efficiency.
YOU CAN DO THAT
You can automate your control signal using the Fisher
Control-Disk
valve from Emerson. Process control loops containing butterfly valves

are often placed in manual mode due to poor control performance. This results in operators
constantly monitoring and adjusting the control signal, significantly reducing efficiency.
With a control range comparable to a segmented ball valve, the Control-Disk valve enables
control closer to the target set point. This allows you to leave your control loop in automatic
mode, regardless of process disturbances. With low maintenance requirements and sizes up to
NPS 36, its time to put the Control-Disk valve in your loop. Visit www.Fisher.com/automatic
to watch an animation video or download a brochure.
Boxscore Construction Analysis
desulfurization units, isomerization units,
sulfur recovery units, amine regeneration
units, vacuum rerun units, delayed coker
units and liquefied petroleum gas (LPG)
treating units.
In mid-December 2012, Foster Wheel-
er was awarded a PMC services contract
valued at $500 MM. Foster Wheeler will
be responsible for all PMC services during
the tendering phase of the main EPC con-
tracts, along with management of the EPC
contractors through completion of perfor-
mance testing. EPC contracts are expected
to be awarded in the second quarter of
2013. Overall completion of the project is
set for 2018.
On the other side of the world, Lake
Charles Clean Energy (LCCE), a subsid-
iary of Leucadia Energy, is investing $2.5 B
in a state-of-the-art plant that will use ad-
vanced gasification technology to cleanly
manufacture industrial products from pe-
troleum coke. The LCCE project, located
at the Port of Lake Charles, Louisiana,
US, will provide clean fuels for the states
domestic petrochemical industry and use
carbon-capture technologies to enhance
domestic oil production. Construction is
scheduled to begin in 2013.
Turner Industries Group is the con-
structor for the project, and KBR will pro-
vide design, engineering and procurement
services. LCCE will acquire petcoke from
Koch Carbon amounting to 7,000 metric
tons of petcoke per day from US Gulf Coast
refiners. LCCE will extract the beneficial
energy from petcoke while avoiding harm-
ful emissions and producing no waste.
In addition to limiting emissions, this
plant is designed to capture, compress and
sell 90% of its CO
2
production. The 4.5
MMtpy of captured CO
2
will be sold for
use in enhanced oil recovery operations
along the US Gulf Coast. LCCE is expect-
ed to be one of the worlds lowest-cost pro-
ducers of methanol and hydrogen, as well
as a low-cost producer of other products
used in the chemical and refining indus-
tries. The LCCE project will be the first of
its kind in the US.
Whether it is lowering sulfur content
in transportation fuels or using gasifica-
tion to manufacture cleaner fuels, refiners
around the world are utilizing new tech-
nologies to create cleaner petroleum prod-
ucts for consumers.
PROVEN EXPERIENCE. TRUSTED RESULTS. WWW.CUDD.COM
Managing turnarounds on time and on budget can present many challenges.
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With a 1.5 million CSF capacity, the Queen Storage tank reduces frequent
deliveries that cause congestion, and can be safely replenished without
interrupting pumping operations, saving you time and money. Equipped
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Detailed and up-to-date information for active construction projects in the refining,
gas processing, and petrochemical industries across the globe|ConstructionBoxscore.com
LEE NICHOLS is director
of Gulf Publishing
Companys Data Division.
He has five years of
experience in the
downstream industry and
is responsible for market
research and trends
analysis for the global
downstream construction
sector. At present, he
manages all data content
and sales for Hydrocarbon Processing Construction
Boxscore Database, as well as all corporate and global
site licenses to World Oil and Hydrocarbon Processing.
For more information about UOP adsorbents, visit www.uop.com/adsorbents.
2013 Honeywell International, Inc. All rights reserved
too late
UOP adsorbents cut your risk of downtime and equipment failure
due to corrosion.
Minimize contamination with proven UOP adsorbents. With a vast portfolio of
molecular sieve and activated alumina adsorbents and as the designer of many
plants in operation today, UOP has been at the forefront of contaminant removal for
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a wide range of adsorbent solutions backed by the support and technical expertise
of a comprehensive team of experts. So dont put your equipment and processes at
risk. Trust UOP for the exact adsorbent solution you need before its too late.
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NEW MAJOR RELEASE!

Viewpoint
PATRICK A. MARFONE is the president of
Chemical and Industrial Services for Baker
Hughes. During his 32 years with Baker Hughes,
Mr. Marfone has held positions such as president
of the Fluids & Chemicals Product Line, president
of Baker Petrolite, vice president and general
manager of the Industrial Division, and regional
manager. Prior to joining Baker Hughes, he
worked for Exxon Co. USA at the Bayway and
Benicia refineries, and at ARCO Chemical Co.,
in Los Angeles, California. Mr. Marfone holds
a BS degree in chemical engineering from the
University of Pennsylvania.
PATRICK A. MARFONE
President, Chemical and Industrial Services, Baker Hughes
Refiners have a new learning curve with shale oil
Weve all heard the news reports:
Shale resource developments have the
potential to make the US energy inde-
pendent for the first time since 1952.
The long-term impact of shale resources
will have far-reaching implications for
everything from US energy policy to
foreign policy. But we dont have to wait
until sometime in the future to reap the
economic benefits of shale developments
relative to hydrocarbon processing, par-
ticularly shale oil.
Second chance for refiners. Liquids-
rich shale plays from North Dakota to
South Texas, and from the East Coast to
the Mid-Continent are reducing energy
costs, adding jobs, and reviving compa-
nies and communities, from mom-and-
pop sandwich shops to crude-oil refiner-
ies that were facing economic shutdowns.
Initially, shale oil seems like a win-win
proposition for refiners. It is a light crude
with low viscosity and low sulfur con-
tenta desirable feedstock for US refin-
ers. Shale oil is increasingly abundant
in many sectors of the US. As a secure
domestic resource, shale oil will enable
refiners to do more accurate long-term
planning. More importantly, shale oil is a
cost-effective crude for refiners.
No good deed goes unpunished. With
all of the pros, there are some cons with
shale oil. A growing number of refiners are
recognizing a pattern of operational issues
when processing crudes from unconven-
tional reservoirs. Since refineries are set
up to handle more conventional crudes,
the unique combinations of challenges
associated with shale oil require refiners
to either accept lower throughputand,
consequently, lower marginsor to look
for ways to improve their shale oil pro-
cessing capabilities so that shale oil can be
refined in more traditional ways.
The composition of shale oil varies
from basin to basin throughout the US.
An analysis of three samples of Eagle
Ford crude delivered to a refiner in one
week showed that the crude density
ranged from 44.6API to 55API. Some
common characteristics can lead to sig-
nificant disruptions across the refining
supply chainfrom transportation from
the oil field to processing at the refinery.
These disruptions cost time and energy,
reduce throughput, and negatively im-
pact refinery economics.
Challenges. Shale oils are often highly
paraffinic crudes. With the highly paraf-
finic shale oils, many shale oils feature
waxes with appearance temperatures as
high as 200F (93C). Consequently, such
crudes can create wax deposits that can
foul transportation modes, storage tanks
and process units. Cold preheat-exchang-
er train fouling is also a potential concern
related to high-melting-point paraffins.
Although the waxy nature of the oils
poses major challenges, the most con-
cerning problem arises in the crude dis-
tillation units, when blending the light,
paraffinic shale oils with heavier crudes.
The resulting asphaltene instability can
create asphaltenic sludge that reduces
capacity in crude tanks, generates emul-
sions in the desalter unit, and fouls pro-
cessing unit preheat exchangers and fur-
nace tubes.
H
2
S control. Shale oils contain hy-
drogen sulfide (H
2
S) and, when treated
with scavengers to curb the presence
of H
2
S, the resulting tramp amines can
partition into the crude-oil phase in the
desalter. These amines can combine with
hydrogen chloride in the atmospheric
column to form corrosive salts. Uncon-
trolled buildup of these salts can reduce
crude unit throughput and reliability.
Profits. A steady diet of shale oil can
also impact margins on the product side.
The paraffinic nature and low sulfur con-
tent of shale oil can lead to cold flow, water
separation and lubricity issues in distil-
late products. Some light-ends products
may experience copper-strip problems,
Viewpoint
and heavy fuel oil stability is sometimes
decreased when shale oil residual materi-
als are blended with asphaltenic stocks.
Solutions. It is clear that, while shale oil
remains a very attractive feedstock for US
refiners, its composition can negatively
impact several steps in the refining pro-
cessfrom transportation to product
shipment. And those complications will
certainly have an adverse effect on refin-
ery margins. The good news is that there
are proven solutions for almost every
step in the process to optimize refining
shale oil and to improve refinery profits.
Field or laboratory testing. For ex-
ample, field or lab testing can help iden-
tify the crude blends at risk of asphaltene
precipitation. A comprehensive evalu-
ation using laboratory desalter bench
testingalong with solids release test-
ing, advanced amine analysis techniques,
and a thorough evaluation of desalter op-
erationscan ensure the best treatment
strategy for a given desalter.
Other predictive tools include a hot-
liquid process simulator for heat ex-
changer simulation, high-temperature
fouling tests (for furnace conditions),
and ionic model technology to simu-
late the corrosive environment so that
the most cost-effective salt mitigation
approaches can be applied. Using ap-
propriate chemical programssuch as
sludge-control additives, contaminant-
removal treatments, antifoulants and
finished fuel additivescan make sig-
nificant contributions to the refinerys
ability to meet operating and product
quality targets while processing noncon-
ventional feedstocks.
Opportunities. Drilling and completing
shale formations do not come without
challenges. Advances in horizontal drill-
ing and hydraulic fracturing, however,
have turned those challenges into oppor-
tunities for operators who are now pro-
ducing from US shale plays. In much the
same way that refiners have responded
to other opportunity crude challenges,
solutions are available that improve re-
finery feedstock selection flexibility and
allow higher rates of shale oil process-
ing, while keeping finished products on
specification, maintaining reliable opera-
tions, reducing costs and improving op-
erating margins.
FIG. 1. Technical assessments both in the
refinery and in the lab are key to developing
treatment programs for shale oil processing.
Sulfur Recovery
Linde Process Plants, Inc.
6100 South Yale Avenue, Suite 1200, Tulsa, Oklahoma 74136, USA
Phone: +1.918.477.1200, Fax: +1.918.477.1100, www.LPPUSA.com, e-mail: sales@LPPUSA.com
A member of The Linde Group
For the past four decades, Linde Process Plants, Inc. (LPP) has designed and/or constructed sulfur
recovery systems. These systems process off gases from gas treating units and sour water strippers.
LPP is a world leader in plant modularization and on-site constructed plants.
Experience
LPP has the experience, specialized skills, impressive track record, and extensive fabrication
facilities to successfully deliver major turnkey process units to global markets.
- Extensive technology portfolio
- Full turnkey capabilities, including process design, detail engineering, fabrication,
construction, and start-up
- Competitive pricing
S 9OOl ce|iec
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Advantages
Linde Process Plants, Inc.
Accepting Challenges. Creating Solutions.

|
Special Report
CORROSION CONTROL
Corrosion is often the root cause of equipment failure, process unit/
plant downtime, off-spec product generation, contamination and
accidents. For the hydrocarbon processing industry, corrosion is
a ubiquitous, ongoing and dynamic process that attacks reactors,
valves, columns, pumps, tanks, piping and other processing
equipment. Better training, maintenance and design practices can
deter conditions that promote corrosion reactions and metal fatigue.
A concentric-ring product is installed at the base of aboveground
storage tanks as part of a cathodic protection solution for large
tank and terminal facilities. Photo courtesy of MATCOR Inc. More
information can be found on page 17.
Special Report
Corrosion Control
S. GHOSHAL and V. SAINIK, Indian Oil Corp. Ltd.,
Mathura Refinery, Mathura, India
Monitor and minimize corrosion
in high-TAN crude processing
High-acid crude (HAC) oils, also called high-total acid
number (TAN) crudes, are oils where TAN [expressed in terms
of milligrams of potassium hydroxide per gram (mg KOH/g)]
is more than 0.5. Acidity is mainly due to the presence of naph-
thenic acids. These crudes trade at discounts of about $3/bbl
to $10/bbl to conventional crudes; therefore, processing these
crudes improves refinery bottom lines. However, processing
high-TAN crudes is also challenging for refineries, especially
those not designed to handle naphthenic crudes.
Refinery asset reliability during high-TAN crude process-
ing is paramount. Hardware changesi.e., upgrading mate-
rials construction from carbon steel (CS) and alloy steel to
stainless steel (SS) 316/317, which contains molybdenum
and is significantly resistant to naphthenic acid corrosion
are complicated tasks for refineries. They call for a large capi-
tal investment as well as a long turnaround for execution. Al-
ternatives to hardware changes are corrosion mitigation with
additives and corrosion monitoring with the application of
inspection technologies and analytical tests.
Corrosion problems during HAC processing are caused by
naphthenic acids. Corrosion is predominant at temperatures
higher than 180C, where shear stress on pipe walls is signifi-
cant. Corrosion problems during the processing of HACs in
the high-temperature section are normally mitigated by dosing
phosphate ester- or sulfur (S)-based inhibitors at certain criti-
cal locations inside the process units. The inhibitors are dosed
in process streams with the help of injection quills.
In addition to inhibitor dosing, intensive corrosion moni-
toring and analytical tests play a major role in equipment and
piping health monitoring and in analyzing stream properties
online. Corrosion-monitoring equipment includes custom-
ized inspection technologies with both intrusive and non-in-
trusive systems.
Naphthenic acid corrosion mitigation. Naphthenic acid
corrosion is determined by TAN, naphthenic acid number
(NAN), temperature, S, velocity (shear stress) and flow re-
gime. During naphthenic crude processing, corrosion at high
temperature is mitigated by injecting either phosphate-based
ester additives or S-based additives. These additives provide an
adherent layer that does not corrode or erode due to the effect
of naphthenic acids.
In HAC processing, higher S content in feed means lower
risk for corrosion. Sulfur has an inhibitive effect. The corrosion
rate has been observed to jump with the same rate of inhibitor
dosing in a changed crude mix (i.e., when low-S crudes with
the same TAN value are processed).
The high-temperature corrosion inhibitor is dosed into the
process streams, normally at a concentration of 3 ppmw15
ppmw. The additive is mixed with the suitable process stream,
typically at a ratio of 1:30. It is injected into the cooled stream
(< 100C) with specially designed corrosion-mitigation quills,
since the inhibitor is highly corrosive to CS, alloy steel and
even SSs. The dosage limit of phosphorous (P)-based inhibi-
tors is decided based on the allowable P levels in the vacuum
gasoils (VGOs) going to hydrocrackers (HCs) and fluid cata-
lytic crackers (FCCs).
Overhead corrosion management. In addition to naph-
thenic acid corrosion at high-temperature sections of units,
overhead corrosion in crude and vacuum units is a major con-
cern. In high-TAN crude processing, acidity increases signifi-
cantly in the overhead of atmospheric and vacuum units, as
these crudes generally contain higher concentrations of salt,
sediments and sometimes organic chlorides.
Desalting these crudes is difficult and, therefore, salt carry-
over to the overhead is more likely during high-TAN crude pro-
cessing. Naphthenic acid molecules at high temperatures also
decompose to form organic acids that become concentrated in
the overhead systems of atmospheric and vacuum units. There-
fore, desalter management and corrosion control and monitor-
ing are critical in the crude distillation unit (CDU), the vacu-
um distillation unit (VDU), and sometimes in the visbreaking
and bitumen units. Desalter residence time, washwater injec-
tion rate, mixing valve differential pressure, and efficacy of the
emulsion breaker all play vital roles in corrosion management.
Corrosion monitoring is normally done using coupons,
electric resistance probes or linear polarization resistance-
based probes that are installed in the overhead line, down-
stream of the air fin cooler or condensers. Chloride (Cl), pH
and iron (Fe) content in the prefractionator and main fraction-
ator overhead receiver are maintained within limits.
Normally, accumulator boot water pH is kept in the range of
66.5; Cl is limited to less than 20 ppm; and Fe is kept below
0.5 ppm. Salt content at the desalter outlet is also monitored
and maintained. For corrosion mitigation, filmer and neutralizer
amine are injected into the overhead. Intermittent washwater
dosing in the overhead to remove salts and corrosive substances
Corrosion Control
is also performed. Many refiners use online analyzers for con-
tinuous monitoring of pH, Fe and Cl. Closed-loop automated
controllers are also utilized to optimize dosing.
Corrosion monitoring by nondestructive testing. Online
corrosion coupons have been widely used in critical process cir-
cuits for the assessment of fluid corrosivity. Normally, alloy-steel
and CS coupons are used for corrosion monitoring.
Coupons can be fixed or retractable. In retractable coupons
at high-temperature locations, a proper sealing system should
be used. Coupons can also be of different shapes and types. The
shape can be rectangular, circular or helical, and may be nor-
mal or pre-stressed. Based on the corrosion rate of coupons (for
both general and pitting corrosion), the corrosive nature of the
fluid can be assessed, and dosing of additives can be optimized.
Electric-resistance probes. Online electric-resistance (ER)
probes are the most widely used, intrusive corrosion-monitor-
ing devices that give the corrosivity of the fluid and measure
corrosion rate in the stream. The ER probes, which are made
of the same metallurgy as that of the main pipe, are inserted
through stubs connected to the pipe. The probes detect the
process fluid and undergo corrosion in the circuit.
The electric resistance of the probe changes with corrosion
and deterioration, and the change in resistance corrosion rate
is measured (FIG. 1). These probes do not measure the exact
corrosion on the pipe; instead, they measure the corrosivity of
the fluid in that particular circuit (FIG. 2). During high-TAN
crude processing, circuits with process fluid temperatures
above 180C are most susceptible to corrosion and, therefore,
ER probes are inserted into these lines.
Normally, these probes are installed at furnace inlet lines
of atmospheric and vacuum units, atmospheric and VGO cir-
cuits, reduced crude oils and short residue circuits. They are
also used in the FCC feed line (preferably in the filter loop)
and the HC feed line (at around 200C, before the charge en-
ters the reactors).
Locations are identified based on the flow conditions and
line geometry. Ideal locations are pump individual discharges,
control valve loops downstream of control valves, near ther-
mowells, etc. Normally, isolatable loops are preferred. A com-
putational fluid dynamics (CFD) study is performed to iden-
tify ideal locations. If the study offers a non-isolatable loop, a
retractable design is selected for the ER probe (FIG. 3).
Refiners are using various advanced versions of ER probe-
based systems that have high levels of accuracy and sensitivity
and that are proven for measuring corrosion in high-temper-
ature lines during naphthenic crude processing. These high-
sensitivity probes have an expected life of three to four years
and will almost instantaneously respond to a 10-mils-per-year
(mpy) change in corrosion rate. Traditional, flush-mounted ER
probes need about a week to detect 10-mpy changes in corro-
sion rate. The thinner the element, the faster the response; like-
wise, the thicker the element, the longer the probe life.
Two forms of probe element are availableflush and cylin-
dricaland there are several mounting configurations to choose
from, the most common of which allows the probes to be insert-
ed and removed under full process operating conditions without
shutdown. Flush probes are used for best thermal performance
where flush mounting with the pipe wall is desirable or essential.
A typical example is a bottom-of-line location. In these applica-
tions, water films commonly collect in the bottom of the line
and are the primary cause of corrosion. The flush probe ensures
that the whole of the probe element is exposed to the water film.
Therefore, it is well suited for CDU and VDU overhead lines.
Cylindrical probes are suited to virtually any aggressive envi-
ronment, since there is no sealing material other than the parent
metal. The measurement area of the element is much greater in
this design and is suitable for use in a single-phase flow.
Field signature methods. In addition to ER probes, nonin-
trusive systems like field signature methods (FSMs) are used
at certain critical locations, such as furnace outlets, transfer
lines, etc., for monitoring the health of equipment and piping
at high temperatures and velocities. These are normally used
where two-phase flow exists at relatively higher temperatures
and inaccessible locations.
FSM corrosion measurements are done directly on the pipe
and fittings, whereas ER probes measure the corrosivity of the
process fluid. FSMs consist of multiple sensors (metallic pins)
that are spot-welded in a rectangular pattern on the pipe/bends
at the most critical locations (FIG. 4). An electric current is passed
from one side of the matrix to the other, and the voltage between
the pins and the critical area is measured. This gives a unique
electric field signature that depends on the geometry and thick-
HK CR
E
R

p
r
o
b
e

r
e
a
d
i
n
g
s
,

c
o
r
r
o
s
i
o
n

r
a
t
e

i
n

m
i
l
s

p
e
r

y
e
a
r
0
5
10
15
20
25
30
VGO RCO
Inhibitor: Nil
3 ppm
6 ppm
9 ppm
12 ppm
15 ppm
FIG. 1. ER probe readings in mpy with change in inhibitor dosing rate
for different process streams during high-TAN crude processing.
Extension adapter
Hollow plug assy
Probe
Pipeline
Corrosion probe system
Access tting body, areweld, buttweld, anged
Heavy protective cover (optional)
FIG. 2. ER probe on pipe during HAC processing.
Corrosion Control
ness of the pipe and the electrical conductivity of the metal. Any
change in field (or signature) resulting from internal corrosion or
erosion is revealed by a change in voltage across the sensor pins.
Online FSM logs are available with permanently installed
data-loggers that collect readings on a real-time basis. They
have a high level of accuracy, and sensitivity is typically on the
order of 0.05%0.1% of pipe wall thickness. The system can be
set up to communicate with the refinery control system so that
data can be reviewed remotely.
A unique advantage of FSM measurement is that it gives area
coverage rather than point measurement. It detects thickness
loss even in the locations between the pins. Advantages of FSM
corrosion rate are that it can be accurately measured at high
temperatures from remote sections of the plant, it provides an
operator to the facility to optimize the corrosion control pro-
gram, and it responds quickly to increased corrosion.
Other nonintrusive techniques. In addition to FSMs, several
other non-intrusive, online monitoring techniques have become
popular in recent years. However, most of these techniques are
ultrasonic-based and, therefore, are point contact-type devices.
This means that they do not cover the entire surface area on
which the sensors are positioned. Some of these systems are spot-
welded, while others are simply clamped and, therefore, can be
moved to other positions. These instruments are generally used
at locations other than furnace outlets and transfer lines, such
as control valve loops and bends at pump discharge (usually on
68-in.-diameter lines) and distillation unit overhead systems.
These alternative nonintrusive systems are often used to
validate ER probe readings over a longer duration. The unique
advantage of such systems is wireless communication. Alterna-
tively, some technologies use permanently installed ultrasonic
probes on pipes and equipment to directly measure thickness.
These instruments can be clamped onto the pipes, and online
data can be gathered.
The main disadvantage of these systems is that they mea-
sure point thickness and do not capture the area. Also, they are
not as accurate or as sensitive as FSMs. However, these systems
can be used in place of ER probes, and they are less expensive
than FSMs.
Hydrogen-permeation method. Aside from ER probes and
FSMs, there are portable instruments that measure hydrogen
(H
2
) flux on the pipe. The basis of this technology is that cer-
tain modes of corrosion in a refinery result in the generation
of atomic H
2
, and, when atomic H
2
diffuses through the metal
wall and permeates outside the pipe wall, this forms a molecule.
By monitoring the changes in H
2
diffusion rate, the variation
of internal corrosion can be inferred. These portable measuring
devices can be used whenever required and can operate at high
temperatures.
Radiography. Conventional and digital radiography are other
proven, nondestructive techniques for assessing piping and
equipment health during HAC processing. Conventional film
radiography can be used as a scanning tool, but it lacks quanti-
tative capability. Radiography is not a 24/7 online monitoring
system, although it has mobility that allows it to be deployed at
a much wider area and at many locations.
In digital radiography, the main advantage is a quantitative
approach that provides for online, condition-based assessment
of risk. Some machines use solid-state X-ray technology in
digital radiography, which is fast, portable and shows the per-
centage of metal loss. It does not require scaffolds or insulation
removal.
Analytical tests. In addition to these equipment reliability-
monitoring systems, analytical tests of process streams are vital
to HAC processing. The monitoring of TAN, NAN, metals and
P is of high importance. TAN and NAN are routinely measured
in different process streams to optimize dosing of inhibitors.
Potentiometric titrators are normally used for TAN measure-
ment, while NAN is measured using the Fourier transform
infrared spectroscopy (FTIR) method. Elementsmainly
metalare monitored with Inductively coupled plasma (ICP)
mass spectrometry or ICP optical emission spectrometry in-
struments. These machines use inductively coupled plasma for
elemental analysis.
Some metals in process streams are measured from a corro-
sion viewpoint. Vanadium (V) and nickel (Ni) are measured to
monitor the content of the heavy metals in VGO streams that
go to the FCC or to the HC, as these are poisonous to FCC
and HC catalysts. Sometimes they also impact product yields.
Additionally, P content in process streams must be moni-
tored. This is because inhibitors for high-TAN crude are P-
FIG. 3. Retractable ER probe installed in process piping at a refinery.
FIG. 4. Pin sensors for FSM welded to bend.
Corrosion Control
based compounds, and there are certain restrictions on the
allowable limit of P in the catalyst of cracker units. A typical
schedule of analytical tests is shown in TABLE 1. A comparison
of several corrosion-monitoring devices used in high-TAN
crude processing is shown in TABLE 2.
Takeaway. Refineries that are not designed for HACs should
install these instruments beforehand and collect base data dur-
ing conventional high-S and low-S crude processing.
These instruments together give a holistic picture regarding
the in-service corrosion and deterioration of equipment during
HAC processing (FIG. 5). Corrosion-mitigation methodology is
finalized after a thorough technical audit of the refinery is un-
dertaken. CFD is also performed during the audit to detect vul-
nerable locations. Refiners can form a multidisciplinary group
consisting of representatives from process, inspection, opera-
tions, quality control and other disciplines for smooth execu-
tion of these activities.
The objective is to minimize risk and reduce metal loss.
However, with this approach, it is relatively safer to limit crude
TAN to 1. Above that level, selective metallurgy upgrading
(e.g., certain bends of high-temperature piping, packed beds,
etc.) is required. With the best of the inhibitors, the corrosion
rate in VGO circuits can be brought down to 78 mpy, which
is still very high compared to the normal corrosion rate at a
refinery. Therefore, a refinery should carry out a thorough risk-
based inspection to further increase the crude TAN level.
SANJIB GHOSHAL joined Indian Oil Corp. in 1997 and is the inspection manager
at the companys Mathura refinery. He holds a degree in metallurgical and
materials engineering from the Indian Institute of Technology in Kharagpur,
India, and has 15 years of experience in inspection and corrosion management.
Mr. Ghoshal specializes in corrosion issues during high-TAN crude processing
in refineries. Other areas of interest include strategic planning for asset-
reliability improvement and risk-based inspection. He has published papers
on corrosion and fouling issues related to cooling water, and the application
of advanced inspection technologies.
VIKAS SAINIK joined Indian Oil Corp. in 2008 and presently serves as the senior
inspection engineer at Indian Oils Mathura refinery. His responsibilities include
inspection and corrosion monitoring at refinery atmospheric and vacuum units.
Mr. Sainik holds a degree in metallurgical and materials engineering from the
Indian Institute of Technology in Roorkee, India, and possesses more than five
years of experience in inspection and corrosion management. Specifically, he
has worked in corrosion management for high-TAN crude oil processing.
TABLE 1. Typical schedule for an analytical test
Stream Analytical test Frequency
Crude tank TAN, S, density,
Fe, Ni, V
Every shift
(three shifts
per day)
NAN Daily
Pre-topping column
bottom
TAN, S, Fe, Ni, V Every shift
(three shifts
per day)
NAN Daily
Heavy kerosine
circulating reux
(HK CR)
TAN, S, Fe, Ni, V Daily
P Daily
NAN Daily
Aviation turbine fuel/aviation
turbine fuel circulating reux
and naphtha
Similar to HK CR Daily
Light GO CR/heavy GO/
reduced crude oil/light
VGO/light diesel oil/heavy
VGO
Similar to HK CR Daily
Vacuum slop/vacuum residue TAN, S, Fe, Ni, V Every shift
(three shifts
per day)
NAN Daily
Vacuum bottoms unit/
bitumen feed
TAN, S, Fe, Ni, V Daily
FCC/hydrodesulfurizer/
HC unit feed
TAN, S, Fe, Ni, V, P Daily
TABLE 2. Comparison of corrosion-monitoring devices used
in high-TAN crude processing
System Online Portable
Non-
intrusive
Directly
measures
wall loss
Where
to use
ER probe Yes No No No Process uid in
single phase;
temperature of
180C300C
FSMs Yes No Yes Yes Furnace outlet
transfer lines
H
2
ux method
No Yes Yes No Any location
required
High-
temperature
ultrasonic
measurements
No Yes Yes Yes As required
Online high-
temperature
ultrasonic
probes
Yes No Yes Yes Substitute
for ER probe
or other xed
corrosion-
monitoring
device
HAC
processing
Lab test
ICP/PT
ER
probes
Fixed corrosion-
monitoring
device
Ultrasonic FSMs
X-ray
Coupons
FIG. 5. A snapshot of inspection techniques and analytical tests.
The Eastern Mediterranean is About
to Take Of. Will You be There?
Gulf Publishing Company invites you to attend the inaugural Eastern Mediterranean Gas
Conference (EMGC) in Nicosia, Cyprus, on 810 April 2013 at the Hilton Cyprus. Noble Energy,
Inc. is the lead sponsor of the event, while Hyperion Systems Engineering is the gold sponsor.
With the development of the Eastern Mediterraneans natural gas industry, Cyprus, Israel and the
surrounding areas are poised to experience unprecedented growth in operations, production,
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At EMGC 2013, executives from operators, service and technology companies active in the
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companies leading development in the area.
Attend EMGC 2013 to:
Get the latest information on the stages of development of exploration, drilling, pipeline
and gas processing projects in the region
Learn more about what oil and gas operators have planned for ofshore Cyprus and Israel
Hear from industry experts about the projected global market impact of the
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Closing Reception
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Keynote Speaker:
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810 April 2013 | Hilton Cyprus, Nicosia | EMGasConference.com
810 April 2013 | Hilton Cyprus, Nicosia | www.EMGasConference.com
AGENDA DAY 1: MONDAY, 8 APRIL 2013
1:305:30 p.m. Doing Business in the Mediterranean
When you register to attend EMGC 2013, you will have the opportunity to register for an optional
pre-conference workshop on Doing Business in the Mediterranean. The workshop will focus on the
regulations and practices guiding business activity in the region and will be supported by the Cyprus
Investment Promotion Agency.
5:307 p.m. EARLY REGISTRATION
811 p.m. VIP Dinner (Invitation only)
AGENDA DAY 2: TUESDAY, 9 APRIL 2013
7:30 a.m. REGISTRATION AND CONTINENTAL BREAKFAST
8:55 a.m. Opening Remarks: John Royall, President and CEO, Gulf Publishing Company
910 a.m. Session One: The Impact of the New Energy Resource
Government of Cyprus: President (invited)
Government of Cyprus: Ministry of Commerce, Industry and Tourism, Cyprus
Government of Israel: Sagi Karni, Head of International Afairs Department and Diplomatic Advisor
to the Minister, Ministry of Energy and Water Resources
Noble Energy, Inc.: Charles D. Davidson, Chairman and CEO
1010:30 a.m. COFFEE BREAK
10:30 a.m.12:40 p.m. Session Two: Resource Potential
Session Chair: Marios Tsiakkis, Secretary General, Cyprus Chamber of Commerce and Industry
Regional Seismic Data Analysis - Pramod Kulkarni, Editor, World Oil
Cyprus Natural Gas, Changing the Picture: Development, Infrastructure and Opportunity - Costas Ioannou,
Natural Gas Public Company (DEFA), Cyprus
Israel Reserves and Production Forecast: Government of Israel
Cyprus Licensing Regulations and Requirements - Marcos Georgiades, Partner, Georgiades & Pelides LLC
Ofshore Regulations: EU Perspective - Jude John Gallagher, Director - Ofshore Technology Business
Development, ABS
Ofshore Regulations: Israel Perspective - Deloitte (invited)
12:401:40 p.m. LUNCH
1:402:40 p.m. Session Three: The Market for New Resources
Managing the Risk of Establishing a Safe and Reliable Design Basis for Natural Gas
Mega Projects - Richard Whitehead, Director, Manchester Advisory Services, Det Norske Veritas S.A.
Regional Potential and Future Projections - Chris Barton, Sr. Vice President, Oil and Gas Business
Development, KBR, Inc.
From Ofshore Gas Fields to Consumption: How to Monetize Resources Efectively - Ricardo Procacci,
General Manager, GE Oil & Gas
2:403:20 p.m. COFFEE BREAK
3:204:40 p.m. Session Four: International Impact
Panel Discussion: The Impact of the New Energy Resource
Panelists: Jim Rockwell, Manager, LNG Technology & Licensing, ConocoPhillips Company; Philip Hagyard, SVP
LNG/GTL Business Unit, Technip; Wak Beydoun, President and CEO, Total E&P Research & Technology USA, LLC
Panel Discussion: A Game Changer for Europe and International Markets
Moderator: Adi Karev, Oil & Gas Leader, Deloitte Worldwide
Panelists: Philip Lowe, Directorate General of Energy, European Commission; Martin Layeld,
Vice President, Gas Consulting, GL Noble Denton; eni (invited)
4:40 p.m. Closing Remarks: John Royall, President and CEO, Gulf Publishing Company
79 p.m. GALA DINNER - Sponsored by Deloitte, Ltd.
Introduction by: Nicos Papakyriacou, Partner in charge of Nicosia Of ce, Assurance and Enterprise
Risk Services, Deloitte, Ltd.
Keynote: Charles D. Davidson, Chairman and CEO, Noble Energy, Inc.
AGENDA DAY 3: WEDNESDAY, 10 APRIL 2013
7:30 a.m. REGISTRATION AND CONTINENTAL BREAKFAST
8:55 a.m. Opening Remarks: Pramod Kulkarni, Editor, World Oil
911 a.m. Session Five: Infrastructure Developments
Panel Discussion: Ofshore Drilling and Production - Future Requirements
Panelists from: EMAS, Ensco (invited), Transocean (invited) and Noble Corporation (invited)
Panel Discussion: LNG/FLNG
Panelists: Victor Alessandrini, FLNG Business Development Manager, Ofshore Business Unit,
Technip; Maximo Hernandez, Managing Partner, Global Oil and Gas, ERM; Woodside (invited)
Panel Discussion: Subsea
Panelists: Jim Byous, President, Ocean Specialists, Inc.; Jean-Pierre Corbel, Eastern Mediterranean
Subsea Commercial Manager, Technip; FMC Technologies (invited); Cameron (invited); Fabrizio Tanzi,
Italy and Eastern Mediterranean Team Leader, GE Oil & Gas
Long and Short of Subsea Pipelines - Uri Nooteboom, President, INTECSEA
1111:30 a.m. COFFEE BREAK
11:30 a.m.1 p.m. Session Six: A Cypriot View
View of Future Developments for Cyprus - Symeon Kassianides, CEO, Hyperion Systems Engineering
Panel Discussion: Infrastructure Requirements
Panelists: Khalid Khadduri, Assistant Vice President, Intermediaries & International Banking, Wealth
and Investment Management, Barclays; Panos Papanastasiou, Professor, Dean of the Engineering School,
Department of Civil and Environmental Engineering, University of Cyprus; George Pelaghias,
Executive Director and Program Coordinator, European Rim Policy and Investment Council (ERPIC)
12 p.m. LUNCH
23 p.m. Session Seven: Israel Perspective
Panelists from Israel Opportunity Energy Resources, LP (invited); Israel Natural Gas Lines Ltd. (invited),
Israel Land Development CompanyEnergy Ltd. (invited) and Israel Electric Corporation (invited)
33:30 p.m. COFFEE BREAK
3:305 p.m. Session Eight: The Future of the Eastern Mediterranean
Terry Gerhart, Vice-President, Operations, Eastern Mediterranean Business Unit, Noble Energy, Inc.
Cyprus - Dr. Charles Ellinas, CEO, Cyprus National Hydrocarbons Company
Government of Israel
5 p.m. Closing Remarks: John Royall, President and CEO, Gulf Publishing Company
Doing Business in the Mediterranean Pre-Conference Workshop
When you register to attend EMGC 2013, you will have the opportunity to register for an optional* pre-conference workshop on
Doing Business in the Mediterranean. The workshop will focus on the regulations and practices guiding business activity in the
region, and will be supported by the Cyprus Investment Promotion Agency.
*Additional fee assessed for workshop attendance.
810 April 2013 | Hilton Cyprus, Nicosia | www.EMGasConference.com
Registration includes:
Two-day conference program (9-10 April 2013) including keynote addresses, general presentations
and panel discussions
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Opening-night formal gala dinner
Option to register for a pre-conference workshop (8 April 2013) on Doing Business in the Eastern
Mediterranean (*additional cost to attend workshop)
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Special Report
Corrosion Control
A. AL-MESHARI, A. ABDELGALIL and S. AL-ENAZI, SABIC
Technology Centre, Jubail, The Kingdom of Saudi Arabia
Mitigate reactor failures due to graphitization
Graphitization occurs in carbon steel (CS) reactors in high-
temperature service (> 455C). As discussed in this case history,
the shell of a methyl tertiary butyl ether (MTBE) reactor became
susceptible to elevated-temperature oxidation that initiated cor-
rosion conditions. In addition, high-temperature fluctuations
fostered stresses that promoted fatigue of the MTBE reactor
shell and, ultimately, caused an emergency shutdown of the unit.
Background. Cracking in the reactor shell of an MTBE unit
was detected by hot-air leaks through the reactor. This failure
resulted in the emergency shutdown. Several investigation
techniques were used to identify the root cause for the failure,
including X-ray fluorescence (XRF), C/S analyzer, optical mi-
croscopy, scanning electron microscope/energy dispersive X-
ray (SEM/EDX), tensile testing and hardness testing. Results
from the thorough investigation identified that the cracking of
the reactor shell was attributed to corrosion fatigue (oxidation
fatigue), due to thermal cycling and graphitization.
Graphitization was the root cause for the degradation of the
steel mechanical properties and for significant reductions in
the fracture toughness, thus facilitating fast crack growth. The
recommendation from this failure and study was the practice to
inspect all reactor shells for graphitization.
The rise in the shell-metal temperature may have been at-
tributed to inefficient thermal insulation provided by the re-
fractory lining. For this MTBE process, the metal temperature
of the reactor should be kept below 427C to prevent graphiti-
zation. The condition of the reactor shells must be evaluated
using metallographic techniques. Ideally, the extent of graphiti-
zation can be investigated through representative sampling for
metallographic examination. Another option is upgrading the
construction material for the reactor shell to a chromium (Cr)-
containing, low-alloy steel.
Definition of graphitization. Graphitization occurs in CS
as an end result from prolonged exposure (over 40,000 hr) to
high-temperature (> 455C) process conditions. It is a process
in which the pearlite decomposes into ferrite and randomly
dispersed graphite. It has been reported that graphitization is
accelerated by high stresses and/or temperature fluctuations.
1
Two types of graphitization were observed in the CS micro-
structurerandom and chain graphitization.
In the random graphitization, the graphite nodules are scat-
tered randomly across the microstructure, leading to degrada-
tion in steel mechanical properties, e.g., strength and hardness.
In the chain graphitization, the graphite nodules form an aligned
structure representing a plane of weakness. Chain graphitization
is usually favored along planes of localized yielding or in regions
that experience plastic deformation due to cold working or
bending. This process leads to considerable reduction in stress-
rupture strength and fatigue resistance of the steel. Furthermore,
chain graphitization can cause a significant reduction in the frac-
ture toughness and, consequently, facilitate fast crack growth.
2,3
Case history. An emergency shutdown of an MTBE unit oc-
curred due to cracking of the main reactor shell. This reactor
had been in service for 15 years, and it is constructed of ASTM
A515 Grade 60 CS and lined with refractory.
In the reactor, isobutene is converted into isobutylene in the
presence of catalyst. In this process, hot isobutene (T 600C)
is fed to the reactor at 170 tph. Then, the reactor is purged with
steam at 250C260C. Finally, hot air (T 675C) flowing
at 630 tph is introduced to regenerate the catalyst. Each cycle
takes about eight minutes.
Investigation. Three plate samples from the reactor shell were
submitted for analysis: A, B and C. Cracks were observed on
the three samples, as shown in FIGS. 13. The cracks appeared
to have initiated at the bolt holes (attached to the shell internal
surfaces) and propagated through the shell plate. Visual exami-
nation of areas near the cracks revealed the presence of multiple
parallel cracks. The internal surfaces of the three samples had
been covered with grayish and reddish deposits that were col-
FIG. 1. General view of reactor sample A. Note: The cracks initiated at
the bolt holes attached to the shell-plate internal surface.
Corrosion Control
lected for chemical analysis. No appreciable wall thinning was
noticed on the three samples.
Material deposit identification. The chemical composition
of the shell material was determined using XRF spectrometry
and C/S analyzer; the results are summarized in TABLE 1. These
materials conform to the chemical requirement for ASTM
A515 Grade 60 CS. The chemical compositions of the deposits
collected from the sample internal surfaces are listed in TABLE 2.
The deposits were composed mainly of iron oxides. Traces of
Al, Si, P, Ca, Mn and Zn were also detected.
Metallographic examination. Cross sections from different
areas of the collected samples were prepared for metallographic
examination. Examination of the steel microstructure revealed
the presence of a high concentration of graphite nodules, as
shown in FIG. 4. These graphite nodules formed aligned struc-
tures, i.e., chain graphitization, in localized areas, as shown in FIG.
5. The SEM/EDX analysis was carried out to confirm the com-
position of the graphite nodules (FIG. 6). The steel was then nital
etched to reveal the microstructure. No cementite was noticed
in the microstructure, thus suggesting that a complete transfor-
mation of cementite in the steel to graphite and ferrite has oc-
curred. Severe, localized chain graphitization was also observed
in several cross sections, as shown in FIG. 7. No creep voids and/
or micro fissures were noticed throughout the microstructure.
Parallel, unbranched wedge cracks, oriented perpendicular
to the surface, were observed on the cross sections removed
from areas near the ruptures (FIG. 8). The cracks nucleated on
the internal surfaces of the shell plate and propagated toward
the external surface. Also, the crack root walls were covered
with dense oxide layers. Some of the cracks have grown through
the graphite particles, suggesting that fatigue resistance was ad-
versely influenced by graphitization, as depicted in FIG. 9.
Mechanical testing. Three round tensile test samples were
machined from each sample. The test was conducted at room
temperature on a universal testing machine. The tensile test
results are summarized in TABLE 3 and FIG. 10. The three speci-
mens from each sample performed fairly consistently. The
results indicated small but definite differences in strength lev-
els among the three different sections of the shell. The steel
strength did not meet the minimum tensile requirements
for ASTM A515 Grade 60 CS. Also, the hardness test results
showed that the hardness of the samples is lower than the mini-
mum hardness requirement (TABLE 4).
FIG. 2. Cracks at the bolt holes were also observed on Sample B.
FIG. 3. Two through-wall cracks were observed on Sample C.
The sample internal surface was covered with reddish layer.
FIG. 4. Optical photomicrograph showing the presence of nodular
graphite across the microstructure, as polished.
TABLE 1. Chemical composition of the reactor shell plates, wt%
C Mn P S Si Al Cr Ni Cu Fe
ASTM A515 Grade 60
4
0.24 (max) 0.98 (max) 0.035 (max) 0.035 (max) 0.130.45 bal
Reactor shell plate 0.13 0.88 0.032 0.006 0.22 0.03 0.03 0.03 0.03 bal
TABLE 2. Chemical composition of the deposits collected
from the sample internal surfaces, wt%
O Al Si P Ca Mn Fe Zn
Sample A 30.4 0.2 0.3 0.1 0.2 0.6 bal 0.3
Sample B 30.2 0.2 0.4 0.1 0.3 0.6 bal 0.2
Sample C 30.1 0.1 0.3 0.1 0.2 0.6 bal 0.3
Corrosion Control
Discussion. The original microstructure of the reactor shells
steel is composed of pearlite (i.e., a mixture of ferrite and ce-
mentite) and ferrite. However, the metallographic examination
(as well as the mechanical testing) showed that the steel under-
went graphitization, and cementite appeared to have complete-
ly decomposed into ferrite and graphite. Random and chain
graphitization were observed throughout the microstructure.
It is obvious that the reactor shell was exposed to temperatures
greater than 455C for extended periods. To control graphitiza-
tion, the metal temperature must be kept below 427C, where
the graphitization rate is extremely low. Overheating of the
reactor shell may be sourced to inefficient thermal insulation
provided by the refractory lining.
The visual and metallographic examinations indicated that
the cracking of the reactor shell was caused by corrosion fa-
tigue (oxidation fatigue) nucleated on the shell internal surface.
Oxidation fatigue is characterized by unbranched, wedge cracks
oriented perpendicular to the surface, and it often appears as
multiple parallel cracks. Indeed, systems that operate cyclically
(e.g., an MTBE reactor) and/or subject to rapid startup and
shutdown procedures are the most vulnerable to oxidation fa-
tigue. Also, the formation of chain graphitization indicated sig-
nificant reduction in fatigue resistance of the reactor shell mate-
rial. The oxidation fatigue process involves these steps:
Thermal cycling causes expansion of the base metal, gener-
ating high internal stresses in the oxide layer. Accordingly, the ox-
ide layer could not withstand high stresses, and, thus, it began to
crack, rendering the metal surface exposed to the environment.
Oxides form on the exposed metal surface at the root of the
crack, creating a notch effect. The next thermal cycle generates
cracking in the oxide along the notch, thus causing the original
crack to deepen.
Repeating the listed steps results in the development of a
wedge-shaped crack propagating through the shell, eventually
leading to a rupture.
FIG. 5. Optical micrograph showing local concentrations of graphite
nodules, i.e., chain graphitization, as polished.
FIG. 6. Backscattered electron image of the graphite nodules and
EDX of the graphite nodules.
FIG. 7. Optical photomicrograph showing a microstructure composed
of ferrite and graphite nodules. Chain graphitization was observed
throughout the steel microstructure as nital etched.
TABLE 3. Tensile test results
Yield strength,
MPa
Tensile strength,
MPa
Elongation,
%
ASTM A515 Grade 60 220 415550 25
Sample A-1 263 361 41.7
Sample A-2 267 359 40.0
Sample A-3 263 355 40.0
Sample B-1 271 375 37.3
Sample B-2 263 370 37.3
Sample B-3 273 376 38.8
Sample C-1 242 342 41.1
Sample C-2 215 347 39.6
Sample C-3 249 344 40.3
TABLE 4. Rockwell hardness test results
Specimen Rockwell, HRB
ASTM A515 Grade 60 6884
Sample A 58.5
Sample B 58.6
Sample C 58.5
Corrosion Control
Lessons learned. With the final root cause identified in the fail-
ure of the MTBR reactor, several recommendations were made:
Monitoring and estimating the shell-metal tempera-
ture is critical when predicting graphitization. The metal
temperature should be kept within the design requirements. It
has been reported that exposure at temperatures below 427C
support an extremely low graphitization rate.
Metallographic techniques should be used to evalu-
ate the condition of the reactor shell. Ideally, the extent of
graphitization can be investigated through representative sam-
pling of the reactor for metallographic examination.
Graphitization may be evaluated using metallograph-
ic field replication procedures. Remember: Damage may oc-
cur in the internal part of the shell wall, making it pointless to
conduct the field replica.
Replacement. If the condition of the reactor shell is
the same as the submitted samples, then the shell should be
replaced. Cracking and ruptures facilitated by graphitization
may occur suddenly and unpredictably, leading to emergency
shutdowns. If graphitization was only found in localized areas
of the reactor shell, then patch repair can be conducted. When
replacing the reactor shell, upgrading the shell material with
Cr-containing low-alloy steel is recommended. Graphitiza-
tion can be prevented by using steels containing more than
0.7% Cr.
Inspect the refractory lining of the reactor. Shell tem-
perature rise can be linked to inefficient thermal insulation
provided by the refractory lining. A refractory specialist should
investigate the performance of the refractory lining inside the
reactor.
NOMENCLATURE
Al Aluminum P Phosphorus
Ca Calcium Si Silicon
Fe Iron S Sulfur
Mn Manganese Zn Zinc
O Oxygen
LITERATURE CITED
1
ASM Handbook, Vol. 1, Properties and Selection: Irons, Steels, and High Performance
Alloys, ASM International, 1993.
2
Foulds J. R., and R. Viswanathan, Graphitisation of Steels in Elevated-Temperature
Service, Journal of Materials Engineering and Performance, October 2001, pp. 484492.
3
Azevedo C. R. F. and G. S. Alves, Failure Analysis of a Heat-Exchanger Serpentine,
Engineering Failure Analysis, December 2005, pp. 193200.
4
ASTM A515/A515M-03 (Reapproved 2007), Standard Specification for Pressure
Vessel Plate, Carbon Steel, for Intermediate- and Higher-Temperature Service.
FIG. 8. Unbranched wedge cracks oriented perpendicular to the
surface and often appearing as multiple parallel cracks, as polished.
FIG. 9. The crack root and walls were covered with oxides. The
cracking of the graphite nodule is near the crack initiation point,
and the crack was transgranular, as nital etched.
FIG. 10. Tensile testing results.
ABDULAZIZ AL-MESHARI is a failure analyst at SABIC
Technology Centre in Jubail, Saudi Arabia. He holds a PhD in
material science and metallurgy from the University of
Cambridge (UK) and an MSc degree in corrosion science and
engineering from UMIST (UK). He is member of a NACE and ASM
member since 2000.
SAAD AL-ENAZI is a failure analyst at SABIC Technology
Centre-Jubail, Saudi Arabia. He holds an MS degree in
manufacturing management and a BSc degree in mechanical
engineering from the University of Toledo.
ABDELGADER ABDELGALIL is a computer simulation
specialist at SABIC Technology Centre in Jubail, Saudi Arabia.
He holds a PhD in solid mechanics from the University of
British Columbia, Canada, and MSc degree in solid mechanics
from Benghazi University, Libya.
Special Report
Corrosion Control
K. RAMESH, Reliance Industries Ltd., Hazira, India
Consider dewpoint corrosion in reactor design
In a unique series of events at an Indian petrochemicals plant,
an 18-mm-thick shell on a 14-month-old oxyhydrochlorination
(OHCL) reactor in a vinyl chloride monomer production unit
suddenly leaked, resulting in a total plant breakdown over the
course of several days (FIG. 1). The cause of the problem was
found to be incorrectly designed external cleats on a hydrocar-
bon reactor. The leak was due to a puncture in the reactor shell
at the bracket support plate (meant for a 5T davit) welded to
the shell (FIG. 2). A similar reactor had been in service for 18
years without any problem.
Technical data and process description. The technical
specifications for the OHCL reactor are shown in TABLE 1. The
function of the OHCL reactor is to make ethylene dichloride
(EDC) by exothermic reaction of ethylene, hydrogen chloride
(HCl) and oxygen (O
2
) in the presence of a fluidized catalyst
[copper (II) chloride and alumina].
Fluidization is induced by feeding air to the bottom of the
reactor after filtration and compression. All streams are fed to
the reactor after sufficient preheating to avoid HCl dewpoint
corrosion in the reactor. The complete section of the OHCL
reactor is shown in FIG. 3.
Observations. A number of observations were recorded dur-
ing the leak response:
The plant was running at a normal, 1,053-metric-ton load
(design capacity is 1,100 metric tons) when the leak was de-
tected, resulting in an emergency shutdown.
A visual inspection revealed localized corrosion of the
shell at the inner diameter. Severe thinning and metal loss were
observed in an area 300 mm wide by 75 mm high, with an orig-
inal thickness of 18 mm (FIG. 4).
The rest of the shell sections were found to be normal, with-
out any significant erosion or corrosion (see FIG. 5 and TABLE 2).
Metallurgical investigations. A chemical analysis of an alloy,
using the optical emissions spectroscopy method, confirmed
the alloy composition to be the specified standard of SA 516
grade 70, with respect to the elements analyzed. The carbon
equivalent of steels used in pressure vessel construction governs
hardenabilityi.e., the extent of microstructural damage to the
material due to welding.
The carbon equivalent, based on alloy composition, was de-
termined to be 0.39, which was within the acceptable limit of
FIG. 1. Leak site at the OHCL reactor.
TABLE 1. Technical specications for the reactor
Specication Measurement
Shell material SA 516 grade 70
Design pressure (max.) 6 kg/cm
2
g (top)
Design temperature (max.) 288C
Operating pressure 3.1 kg/cm
2
g (top)
Operating temperature 226C (top)/245C (bottom)
Service EDC + HCl + C
2
H
2
+ O
2
+ CO
2
FIG. 2. A puncture in the reactor shell at the bracket support plate
was found to be the source of the leak.
Corrosion Control
0.43 for the specified standard. Also, a tensile test showed satis-
factory physical property conditions meeting the requirements
of SA 516 grade 70 material. The hardness of bulk materials was
found to be within acceptable limits.
Micro-hardness measurements revealed the highest values
(210 Vickers hardness number) at the fillet weld, which was
determined to be normal. An impact test performed at 46C
showed acceptable values. Nondestructive testing by wet fluo-
rescent magnetic particle inspection on both the inner and outer
surfaces did not detect any linear indication, and no cracks were
observed around the leakage. Ultrasonic flaw detection suggest-
ed that the plate was free from significant internal defects.
Macrostructural observation discovered a bright band of
heat-affected zone (HAZ) beneath the fillet weld, along with
dark streaks at the center of the cross-section. The welding
was determined to be internally sound and absent of any sig-
nificant defects. Observation of the microstructure indicated
fine-grained banded ferrite and a pearlite structure to the plate
material. Welding on the external surface showed a microstruc-
ture comprising of a dendritic structure of ferrite and carbides,
whereas the HAZ microstructure showed a fine and coarse-
grained ferrite and pearlite structure. No significant abnormality
in the welding was observed.
The microstructure of the inner diameter of the reactor clear-
ly showed the effects of erosion and corrosion. In some places,
preferential corrosion of the pearlite phase was observed. The
scale formation was observed at a microlevel all over the inter-
nal surface. The microstructure of the outer diameter showed
no significant degradation or damage. Scanning electron micros-
copy (SEM) of the inner surface revealed a defined corrosion/
erosion pattern, although the surface was found to be free from
cracking (FIG. 6).
Conclusion from metallurgical investigations. The steel
alloy shell plate showed acceptable conditions for chemical
composition, strength, toughness and microstructure proper-
ties. The puncture was located at the fillet weld toe of a brack-
eta localized region.
FIG. 4. A visual inspection revealed severe thinning and metal loss. FIG. 3. The complete section of the OHCL reactor.
Corrosion Control
Damage was not observed on side-support fillet welds on the
same bracket; nor was it observed on other shell plates where
pressure, temperature and fluid conditions remained constant
at the same elevation inside the reactor. None of the other fillet
welds located at the same elevation outside of the shell showed
evidence of material degradation underneath. This suggested
that a localized phenomenon was affecting the shell plate, leading
to erosion and corrosion of the surface of the reactor. The logical
next step was to find the reason for the concentrated metal loss.
Detailed calculations estimated the heat transfer and resulting
temperature profile in the davit support welded to the OHCL
reactor. The basis of the study used a process temperature in the
reactor of 220C, with normal process fluid composition, and an
ambient temperature of 30C.
Basis for calculations. In the steady state, some of the heat
contained in the reactor effluent gases upstream of the cyclones
is lost through the reactor wall to the atmosphere. With a heat
balance, the heat loss from the process fluid to the wall equals
the heat transmitted through a fouling layer (if present); the
heat transmitted through the wall equals the heat transmitted
through the insulation (if present), which equals the heat loss to
the air, as shown in Eq. 1.
Q/A = h (t
ip
t
f
) = h (t
ff
t) = k
iw
(t t
io
)/x =
k
w
I (t
o
t
I
)/x
I
= h
a
(t
I
t
a
)
(1)
where:
Q/A= heat loss per unit area.
FIG. 7 shows a sketch of the davit support and reactor wall
showing the legend for the different temperatures and distances
used in the calculations. The thermal conductivities for carbon
steel at 225C and glass-wool insulation at ambient temperature
are shown in Eqs. 2 and 3:
k
w
= 47 W/mK (2)
and
k
I
= 0.035 W/mK (3)
In this case, when estimating the highest shell temperature
for the steady-state condition, no fouling was assumed. Any
buildup of fouling acts as insulation and further lowers the
shell temperature.
Deposits were discovered, but the thickness was unknown.
The area around the davit support was insulated to the same
thickness as the shell of the reactor (insulation thickness of 100
mm), but the davit support itself was an uninsulated metal fin-
ger attached to the shell wall. The davit support acts like an air-
cooler fin, increasing the surface area available for heat transfer.
The total heat loss through the davit support is the sum of the
heat transferred directly from the process to the shell wall be-
hind the support, along with the heat transferred to insulated
sections of the shell in the surrounding areas, and then trans-
mitted through the wall to the supportthe coldest spot.
Heat-transfer coefficients. In an air-based reactor, the reac-
tor gas effluent has a significant concentration of nitrogen. For
simplification purposes, the formula for the heat-transfer coef-
ficient for nitrogen is also used for the process gas.
For convection to and from a vertical plate (e.g., a reactor
wall), the heat-transfer coefficient is h
c
= 0.19 (t
p
t
i
)
0.33
, where
TABLE 2. Thickness measurements for shell sections, mm
Region Thickness Region Thickness Region Thickness
A 19.2 M 19 Y 18.2
B 19.2 N 17.2 Z 18.2
C 13.7 O 17.2 A1 18.7
D 13.7 P 17.2 B1 18.7
E 13.7 Q 18.2 C1 18.4
F 17.9 R 18.2 D1 18.4
G 19.7 S 17.9 E1 18.3
H 5.3 T 17.1 F1 18.3
I 5.3 U 17.1 G1 18.8
J 5.3 V 17.1 H1 18.8
K 5.3 W 18.2 I1 18.9
L 17.9 X 18.2 J1 18.9
FIG. 5. Plot showing corroded shell sections.
FIG. 6. This SEM image shows pit holes similar to those found
in corrosion patterns.
Corrosion Control
Calculations for top davit support as installed
t
p
= 211C = 412F
t
a
= 30C = 86F
Wall thickness = 18 mm
Width of support = 454 mm
Height of support = 30 mm
Insulation thickness on reactor = 100 mm
Length of support = 504 mm
Distance to hole = 162 mm
Diameter of hole = 277 mm
K
wall
= 47 W/mK at 225C
K
ins.
= 0.035 W/mC at ambient
Cross-section of shell behind support = 0.01362 m
2
Surface area of support exposed to air = 0.4332 m
2
h
c
= B3 d
t
0.33
Btu/ft
2
hF, t = F
B3
h
= 0.22
B3
v
= 0.19
Estimate temperature profile without hot metal heat input
h
r
= (T
4
T
u
4
) (T
T
u
)
= 0.95, T = R
Estimate t
o
= 34.5C = 94F
t
ref
= 273.16 K
= 5.67 10
8
W/m
2
K
4
h
r
= 6.1382 W/m
2
K
1 W/m
2
C = 0.176 Btu/ft
2
h F
1.73 10
9
Btu/hft
2
R
4
h
c
= 2.49 W/m
2
K
h
a
= 8.63 W/m
2
K
Q
o
= 16.8 W
t
i
(C) = 38.7447C
(Q /A)
a
= 38.8 W/m
2
, due to larger surface
For inside, h
c
= 7.17 W/m
2
K
Q
i
= 16.8 W
Iterate estimate t
o
until Q
o
= Q
i
(Q/A)
p
= 1234.78 W/m
2
through small cross-section
Neglecting any heat input from nearby hot metal, the
shell behind the support is 38.7C
Estimate hot shell temperature for insulated sections
of reactor
Estimate t
l
, 36.2C = 97F
h
r
= 6.1892 W/m
2
K
Radiant heat transfer is much higher than conductive
to atmosphere
h
c
= 2.77 W/m
2
K
h
a
= 8.96 W/m
2
K
(Q /A)
a
= 55.3 W/m
2
t
o
= 194C
t
i
= 194C
For inside, h
c
= 3.31665 W/m
2
K
(Q /A)
p
= 55.3 W/m
2
Iterate estimate t
l
until (Q /A)
a
= (Q /A)
p
Try to estimate heat transfer from hot shell wall to cold
davit support
Areas for heat transfer from various sources, m
2
:
0 From process gas = 0.01362 m
2
0 From side metal = 0.00054 m
2
0 From top/bottom = 0.008172 m
2
Add heat duties from all sources and check resulting
metal temperature to atmosphere
Estimate t
o
= 102.545C
Q
p
= 10.5887 W
Q
s
= 16.7241 W
Distance to hole = 278.588 mm
Q
t
= 218.291 W
Q
b
= 218.291 W
Total duty = 463.90 W
Iterate t
o
until Q
total
= Q
a
h
r
= 8.5223 W/m
2
K
h
c
= 6.24 W/m
2
K
h
a
= 14.8 W/m
2
K
Q
o
= 463.891 W
t
i
= 110.5C
In still air (no rain), the inside shell wall temperature
is around dewpoint
In rain, much more heat can be removed, lowering
the wall temperature to below dewpoint
Calculations for thinner (20-mm) top davit support
t
p
= 211C = 412F
t
a
= 30C = 86F
Wall thickness = 18 mm
Width of support = 454 mm
Height of support = 20 mm
Insulation thickness on reactor = 100 mm
Heat-transfer calculations used in case study
Temperatures:
t
p
= Process temperature, = 211C = 412F
t
i
= Inside metal temp., C = outside metal temp., C
t
I
= Insulation surface temp.,C (when present)
t
a
= Ambient temperature, = 30C = 86F
Goal: Estimate temperature prole in davit support
Sketch of davit support
Dimensions:
a = wall thickness, mm = 18
b = support height, mm = 30
c = support length, mm = 504
d = support width, mm = 454
e = distance to hole, mm = 162
f = hole diameter, mm = 277
g = insulation thickness = 100
a
b
e
f
c
d
g
t
o
t
p
t
i
t
o
t
a
t
I
FIG. 7. Calculations used for heat-transfer measurements.
Corrosion Control
h has units of Btu/ft
2
hF and t has units of F. For convection
from a horizontal plate (e.g., a davit support), the heat-transfer
coefficient is h
c
= 0.22 (t
o
t
a
)
0.33
, where h has units of Btu/
ft
2
hF and t has units of F. For the heat transfer to air, radiation
is also involved. The heat-transfer coefficient h
a
is the sum of
the convection and radiation heat-transfer coefficients; i.e., h
a
=
h
c
+ h
r
. The radiation heat-transfer coefficient is h
r
= (t
o
4
t
a
4
8) (t
o
t
a
), where = 0.95 and = 5.67 10 W/m
2
K
4
9,
or 1.73 10 Btu/h ft
2
R
4
. The emissivity, , in chemical plants is
usually taken to be 0.900.95 because clean and bright surfaces
are rapidly dulled by corrosion, chemicals, etc. In this case, 0.95
has been assumed; is the Stefan-Boltzmann constant.
Calculations for heat transfer. While the area of the shell
wall behind the davit support is well-defined for use in calcu-
lating the heat transmitted to and through the reactor wall, the
top davit support is an irregular horizontal piece of metal.
To simplify calculations, the support is assumed to be a rect-
angular piece with dimensions of 454 mm by 504 mm, with a
277-mm-diameter hole in it (see sketch in FIG. 7). The vertical
sections of the support are ignored, as is the surface area of the
davit itself, which represents a much larger area for heat trans-
fer to the atmosphere. For heat transfer through the support,
a representative distance is also needed. The distance to the
hole is taken to represent an average distance for heat transfer
through the support to the atmosphere.
Using these assumptions, the calculation results are expect-
ed to be conservative; i.e., they will show a higher inside shell
wall temperature. The first calculation step is to estimate the
temperature profile when considering only heat input from
the process and neglecting heat input from the adjacent, insu-
lated hot shell. Since the heat-transfer coefficients are related
to the temperature difference, the temperature on the outside
of the support must be estimated, and then the heat transfer
to the atmosphere is calculated. The heat transfer to the atmo-
sphere is then compared to the calculated heat transfer from
the process to the reactor shell behind the support. When
both heat quantities match, the estimated temperature profile
is calculated.
Length of support = 504 mm
Diameter of hole = 277 mm
K
wall
= 47 W/mK at 225C
K
ins.
= 0.035 W/mC at ambient
Cross-section of shell behind support, 0.00908 m
2
h
c
= B3 d
t
0.33
Btu/ft
2
hF, t = F
B3
h
= 0.22
Surface area of support exposed to air = 0.4012 m
2
B3
v
= 0.19
Estimate temperature profile without hot metal
heat input
h
r
= (T
4
T
u
4
) (T
T
u
)
= 0.95, T = R
= 5.67 10
8
W/m
2
K
4
Estimate t
o
= 33.4C = 92F
t
ref
= 273.16 K
h
r
= 6.1037 W/m
2
K
1 W/m
2
C = 0.176 Btu/ft
2
hF
1.73 10
9
Btu/hft
2
R
4
h
c
= 2.26 W/m
2
K
h
a
= 8.37 W/m
2
K
Q
o
= 11.3 W
t
i
(C) = 37.6281C
(Q /A)
a
= 28.1 W/m
2
, due to larger surface
For inside, h
c
= 7.18 W/m
2
K
Q
i
= 11.3 W
Iterate estimate t
o
until Q
o
= Q
i
(Q /A)
p
= 1,245.44 W/m
2
through small cross-section
Neglecting any heat input from nearby hot metal,
the shell behind the support is 37.6C
Estimate hot shell temperature for insulated sections
of reactor
Estimate t
l
= 36.2C = 97F
h
r
= 6.1892 W/m
2
K
Radiant heat transfer is much higher than conductive
to atmosphere
h
c
= 2.77 W/m
2
K
h
a
= 8.96 W/m
2
K
(Q /A)
a
= 55.3 W/m
2
t
o
= 194C
t
i
= 194C
For inside, h
c
= 3.31665 W/m
2
K
(Q /A)
p
= 55.3 W/m
2
Iterate estimate t
l
until (Q /A)
a
= (Q /A)
p
Estimate heat transfer from hot shell wall to cold
davit support
Areas for heat transfer from various sources, m
2
:
0 From process gas = 0.00908 m
2
0 From side metal = 0.00036 m
2
0 From top/bottom = 0.008172 m
2
Add heat duties from all sources and check resulting
metal temperature to atmosphere
Estimate t
o
= 104.91C
Q
p
= 6.91997 W
Q
s
= 10.8621 W
Distance to hole = 278.588 mm
Q
t
= 215.333 W
Q
b
= 215.333 W
Total duty = 448.45 W
Iterate t
o
until Q
total
= Q
a
h
r
= 8.6174 W/m
2
K
h
c
= 6.31 W/m
2
K
h
a
= 14.9 W/m
2
K
Q
o
= 448.455 W
t
i
= 114.662C
For the thinner support, the inside shell wall
temperature is 4.2C higher
Therefore, the thicker top support shell wall
temperature will reach dewpoint first
Corrosion Control
48
As shown in FIG. 7, the inside temperature of the shell is about
39C in this case. One interesting result is that, for heat transfer
to the atmosphere from the bracket, the radiant contribution is
much higher than the conductive contribution. Also, the larger
surface area available for heat transfer reduces the temperature
difference for transmitting a specific amount of heat, compared
to the surface area of the shell behind the support.
The second calculation step is to estimate the temperature of
the insulated hot shell that surrounds the support. A similar pro-
cedure is followed, this time with another layer (the insulation)
through which heat passes. The temperature of the insulated hot
shell is estimated to be 203C.
The third calculation step is to estimate the total heat transfer
from all sources, from the support to the atmosphere. Besides heat
transfer from the process to the support via the shell, heat comes
from the hot shell from the sides, the top and the bottom of the
support. The cross-sectional areas for each source differ due to ge-
ometry, and the distance from the sides to the hole is greater than
the distance from the process to the center of the top and bottom.
During this procedure, the sum of all heat inputs flowing
through the support is compared to the sum of the heat loss to
the atmosphere from the support. At an outside wall tempera-
ture of 106C, at the selected representative distance, there is a
heat balance. The resulting inside shell wall tempera-
ture is calculated to be 114C.
To investigate why only the top davit support hori-
zontal section (the thickest metal plate) was corroded,
the same calculation was made using a 20-mm-thick
davit support horizontal section. Calculations with the
thinner support showed that the estimated inside shell
wall temperature was about 118C, which was about
4C higher than with the thicker plate.
Therefore, for any given reactor operating conditions, the
thicker metal plate will reach the dewpoint before the thinner
plate. A simulation is then made to check the expected dew-
point temperature, cooling the reactor effluent composition to
the dewpoint at the operating pressure of 3.9 kg/cm
2
g. The re-
sulting dewpoint temperature is 109C.
It is possible that the heat-transfer coefficient for rain falling
on the bracket is 5 to 50 times that of the radiant, plus convec-
tion transfer to still air. Additional calculations are performed
to define the range of the inside metal temperatures that will re-
sult. At five times the heat transfer of still air, the rain decreases
the calculated inside metal temperature to approximately 71C.
At 50 times the heat transfer of still air, the calculated inside
metal temperature drops to approximately 49C.
Discussion of results. The average inside shell wall tem-
perature for the whole horizontal davit support was calculated
to be very close to the estimated dewpoint. Therefore, it was
likely that, during some combination of actual operating con-
ditions, the coldest spot behind the davit support bracket (the
center) had reached the dewpoint and initiated condensation
from the process gas. The process gas contained a significant
concentration of water (1 mole per mole of EDC produced)
and traces of unreacted HCl. Since HCl is easily absorbed in
liquid water, the drops of water condensing at the cold spot
will have a high HCl concentration, making them very corro-
sive to carbon steel.
During periods of rainfall, the heat-transfer coefficient due
to the rain is at least five times higher than the natural convec-
tion to air. Therefore, the metal temperature is calculated to
drop significantly below the dewpoint. This will initiate the
corrosion process if it does not begin during normal operation.
Once the corrosion process starts, corrosion products (such as
iron oxide) building up on the metal surface may act like a foul-
ing or insulating layer, which will also lower the metal tempera-
ture behind the fouling.
Catalyst fines in the process gas are present in this area of
the reactor. It is possible that catalyst particles come into con-
tact with the condensed droplets and become sticky and ad-
here to the metal surface. This wet catalyst can become a nu-
cleus for further corrosion by absorbing water/HCl, while also
acting as an insulating layer. This interpretation seemed to be
supported by the energy dispersive spectroscopy analysis. The
catalyst was copper chloride supported on an aluminium oxide
base, while corrosion products were largely metal oxides, with
some chlorides.
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Once the corrosion process starts, corrosion
products building up on the metal surface
may act like a fouling or insulating layer.
Corrosion Control
The black deposit, which was furthest away from the hole,
showed some aluminium and some chloride. It also showed
some catalyst deposit on the cyclones and coils, which appeared
to be a normal occurrence in most parts of the reactor. The red
deposit, which was below the hole, gave a high concentration
of oxygen, likely from the transportation of corrosion products
with the condensate and their deposition when the condensate
vaporized again.
The catalyst quantity in this area was not much different from
the black deposit, since the aluminium content was similar. The
yellow deposit, closest to the hole, seemed to have a higher cata-
lyst content, since the aluminium content was more than double
that of the other samples. It also had high oxygen content, indi-
cating corrosion products in this area as well.
The shape of the corroded area, which mirrored the horizon-
tal section of the support, was likely due to condensed droplets
running down to a hot section of the shell, then vaporizing again,
so that only the cold metal behind the support was affected. The
coldest part of the horizontal section was the center, which was
the furthest distance from the adjacent insulated hot sections. The
corrosion was likely to have started here and then spread uniformly
toward the edges of the cold region. Additionally, any signs of ero-
sion can be explained by the action of the catalyst fines in the gas
acting like sand blasting, once a hole in the shell was created and
process gas began flowing out as a result of the pressure difference.
The thermal calculations support the theory that a cold spot
in the top davit support initiated dewpoint corrosion, which
led to the hole in the shell. Regarding possible erosion from the
process gas in normal operation, the two sets of cyclones were
symmetrically arranged, with inlets 180 from each other. Any
set of flow conditions was expected to affect both sides of the re-
actor equally, while the shell damage was restricted to one loca-
tion. Since it was not expected that the reactor operated outside
of normal fluid velocities, dewpoint corrosion was likely the
cause of the hole in the shell.
Having verified the inadequacies of design and the root
cause, the davit supports were shaved off and the shell was com-
pletely insulated. No additional problems were encountered in
the reactor.
Recommendations. To avoid cold spots and dewpoint cor-
rosion in such a reactor service, it is not recommended to have
large, uninsulated parts welded to the shell of the reactor. Con-
versely, if these parts are present, they should be properly en-
gineered at the design stage to avoid potential cold-spot issues
in service.
K. RAMESH is the vice president of mechanical and central
engineering services at Reliance Industries Ltd. in Hazira, India.
He has over 20 years of experience in all aspects of static
equipment inspection, design, nondestructive testing, failure
analysis, material selection, quality assurance, corrosion
monitoring and control, and welding inspection. Mr. Ramesh
holds a masters degree (MTech) from the Indian Institute of
Technology in Kharagpur, India. He is a certified inspector for API-510, API-570,
API-653, AWS-CWI and ASNT Level-II RT/PT/MT/UT.
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Special Report
Corrosion Control
T. HANRATTY, The Sherwin-Williams Co., Houston, Texas
Corrosion under insulation is a hidden problem
Corrosion under insulation (CUI) is
one of the costliest avoidable problems
facing the hydrocarbon processing in-
dustry (HPI) today. CUI afflicts refiner-
iesspecifically, the steel piping, storage
tanks, container vessels and other pro-
cess equipment within the plants that are
subject to extreme temperature fluctua-
tions. Calcium silicate or mineral-wool
insulation applied to the pipe or vessel
can mitigate the thermal cycling effects.
But the presence of seams, gaps or other
discontinuities in the insulation layer
makes them susceptible to infiltration by
outside moisture or from the process en-
vironment itself.
Understanding the mechanisms.
CUI originates when water and contami-
nants infiltrate an insulated system that
has certain water retention, permeabil-
ity and wetability characteristics. Water
sources include rainfall, cooling tower
drift, steam discharge, wash downs and
(because insulation is not vapor tight)
condensation. Water may enter the sys-
tem due to breaks in the waterproofing,
inadequate system design, incorrect in-
stallation, poor maintenance practices or
a combination of such factors.
Once wet, the insulation systems
weather barriers and sealants trap the wa-
ter inside, so the insulation remains moist.
Next to the equipment surface, the insu-
lation forms an annular space or crevice
that retains the water and other corrosive
media. For example, chlorides and sul-
fates that may be native to the insulation
can accelerate the corrosion process.
Substrates of either carbon steel (CS)
or austenitic and duplex stainless steel
(SS) are susceptible to CUI. In CS, CUI
occurs in piping or equipment with a skin
temperature in the range of 25F to 350F
(-4C to 175C), where the metal is ex-
posed to moisture over time under any
kind of insulation. The rate of corrosion
varies with the specific contaminants in
the moisture and the temperature of the
steel surface. Waterborne chlorides and
sulfates concentrate on the CS surface as
the water evaporates.
In austenitic and duplex SS, external
stress corrosion cracking (ESCC) can oc-
cur, but the temperature threshold is high-
er, from 120F to 350 F (50C to 175C).
For ESCC to develop, sufficient tensile
strength must be present. Here again,
waterborne chlorides concentrate on the
SSs hot surface as water evaporates.
Why CUI is a hidden problem. Once
infiltration occurs, insulation and clad-
ding conceal the progress of degradation
to piping and equipment. Even with ob-
servation ports, less than 1% of the sur-
face is visible, and those areas generally
are not representative of the whole unit.
Removal of just some insulation to com-
plete a minor repair job can lead to the
discovery of a degree of corrosion that is
an unpleasant surprise and may require a
facility shutdown to rectify.
Typically, insulation is removed on a
1520 year cycle, which makes diagnos-
ing a problem in a timely manner less
likely. Yet, because in existing facilities
pipes and vessels may have been put into
service when coatings, insulation and re-
finery operating conditions were very dif-
ferent than they are today, it is all the more
critical to promptly identify deterioration
lurking on these substrates.
The evolution of the CUI problem
goes back to the 1970s. Before that time,
little if any thermal insulation was ap-
plied to heated CS equipment and ves-
sels below 300F (150C). But as energy
costs increased, it became more cost-ef-
fective to apply insulation. Concurrently,
newer processes came onstream, operat-
ing at higher and often cyclic tempera-
tures while austenitic SS pipe and equip-
ment became more common as well.
Together, these developments dramati-
cally increased the amount of insulation
used in the HPI and set the stage for CUI
to become a pervasive issue.
Chronic CUI has also become a
problem for reliability engineers. Major
equipment outages, whether for periodic
inspection and maintenance or due to a
catastrophic failure, account for more
operational disruptions than any other
cause. Understandably, all of the major
HPI companies became aware of and
were concerned about the problem, with
Although it is common in the petrochemical and refining industries to use a
shop-applied inorganic zinc (IOZ) coating as a primer on new CS piping (be-
cause it dries quickly and is cost effective), IOZ provides inadequate corrosion
resistance in closed, sometimes wet, environments. At temperatures greater than
140F (60C), the zinc may undergo a galvanic reversal, where the zinc becomes
cathodic to the CS. Shop-primed pipe will be finish-coated at the jobsite, depend-
ing on the service conditions needed.
The NACE standard recommends topcoating the IOZ to extend its service
life, and that it not be used by itself under thermal insulation in service tempera-
tures up to 350F (177C) for long-term or cyclic service. In cases where pipe is
previously primed with an IOZ coating, it should be topcoated to extend its life.
Topcoating recommended
Corrosion Control
one taking the lead in thoroughly ana-
lyzing the mechanisms of corrosion and
developing test protocols for protective
coatings to deal with it.
Protective coatings. Though valiant
efforts to keep water out of insulated
systems can be made using different
design materials and configurations of
the equipment to be insulated, CUI is
not usually kept at bay on the strength
of those measures alone. Industry guid-
ance, provided by NACE International,
The Corrosion Society, holds that im-
mersion-grade protective coatings are
the best defense against CUI in both in-
sulated CS and austenitic and duplex SS.
Insulated steel capable of trapping water
is considered to be under immersion at
210F (99C) or higher.
NACE Standard SP0198-2010, The
Control of Corrosion Under Thermal
Insulation and Fireproofing Materials
A Systems Approach, reflects the latest
insights in CUI prevention and mitiga-
tion from the oil and gas industry, includ-
ing the products and systems available to
combat CUI that have a track record of
success. And many of the insights stem
from the shift of oil and gas exploration,
extraction and processing to offshore
deepsea locations around the world.
This shift has numerous implications
for those entrusted with protecting float-
ing production, storage and offloading
(FPSO) assets from corrosion, in general,
and CUI, in particular. The marine envi-
ronment combined with extreme process
temperature fluctuations can accelerate
the corrosion rate of process equipment
and CS process piping and vessels under
insulation by a significant factor com-
pared to onshore assets.
So, while in the past CUI was once
largely a maintenance issue in existing re-
fineries, the dominance of offshore new
construction and conversions demanded
new strategies for asset protection. Own-
ers expect their vessels to have decades-
long life cycles without dry docking. And
specification of coatings has become a
high-level decision, given what is at stake.
Given such customer demand, the
protective coatings industry has devel-
oped products that can accommodate
not only extended life cycle expectations,
but also the dramatic increase in steel fab-
rication work to produce the equipment
and vessels.
Research and development is key.
Ten years ago, the typical process operat-
ing temperatures of insulated equipment
were lower than they are today. Modern
facilities operate at temperatures as high
as 400F (205C), where 300F (150C)
was more the norm previously. Although
most equipment doesnt run at the high
end of the temperature design, spikes can
occur for various reasons and must be
taken into account when specifying the
appropriate coating system. Thus, a cru-
cial consideration when determining the
appropriate protective coating system to
use under insulation is the expected ser-
vice temperature of the equipment or pip-
ing, especially when intermittent thermal
cyclingfrom hot to ambient or hot to
less hot temperaturesis present.
Present commercially available coatings
are engineered to perform at various tem-
perature ranges because one size does not
fit all. Phenolic epoxies are for tempera-
tures of 50F to 300F (45C to 150C);
Novolac epoxies should be applied for
temperatures of 50F to 400F (45C to
205C); and inert multipolymeric matrix
coatings are best for temperatures from
50F to 1,200F (45C to 650C).
Coatings suitable for refinery applica-
tions should perform well in testing pro-
tocols based on both accelerated and real
world scenarios involving typical CUI
mechanisms. Chief among these is the
boiling water test, which is the gold stan-
dard for accelerated testing of
heat-resistant coatings. To en-
sure a coating can offer supe-
rior resistance to thermal cy-
cling, a steel panel is subjected
to thermal shock in a simu-
lated immersion scenario. The
best results show no adhesion
or blistering after 80 cycles of
the test when applied at ambi-
ent temperatures.
But these coatings have to
endure more than just cor-
rosion. Manufacturers of
second-generation CUI coat-
ings recognize that products
must address the challenges stemming
from new construction. Now coatings
must offer enhanced shop coating and
throughput properties; durability during
transportation and erection of fabricated
modules; and worker friendliness in a
shop environment.
This means more flexible coatings,
with harder films, that deliver measurable
reductions in dry-to-recoat and dry-to-
touch times; better impact resistance to
limit damage in transport from the shop
to the jobsite; and lower volatile organic
compound emissions to promote worker
safety. With these attributes come a re-
duced total cost of ownership and extend-
ed service life for high heat applications
and equipment under insulation.
Coatings that demonstrate these addi-
tional attributes will perform well in rig-
orous testing protocols based on ASTM
standards for abrasion and impact resis-
tance, such as the falling sand, Taber abra-
sion and pencil hardness tests. These tests
are done under similar ambient tempera-
ture conditions to the ones used in the
boiling water test.
TIM HANRATTY is petrochemical business
development manager and a corrosion specification
specialist for The Sherwin-Williams Co. in Houston,
Texas. He is a NACE-certified CIP Level 1, Level 2 and
Level 3 Peer Review Coating Inspector. Mr. Hanratty
was a member of the committee that developed NACE
Standard SP0198-2010.
Once infiltration occurs, insulation and cladding conceal
the progress of degradation to piping and equipment.
Even with observation ports, less than 10% of the surface
is visible. Removal of just some insulation to complete
a minor repair job can lead to the discovery of a degree
of corrosion that is an unpleasant surprise and may
require a facility shutdown to rectify.

|
Bonus Report
SAFETY DEVELOPMENTS
Safety programs are part of best practices implemented by
hydrocarbon processing facilities and are central to improving
plant and company profitability. More importantly, safety
programs must be able to adapt to the needs of each facility,
and they require support from top management down to factory-
floor personnel.
Engineers work with an operator training simulator. See full story
in the February 2013 Hydrocarbon Processing article, Operator
training simulators for brownfield units offer many benefits,
pp. 4547. Photo courtesy of Honeywell Process Solutions.
Bonus Report
Safety Developments
M. A. TURK and A. MISHRA, Invensys Operations
Management, Houston, Texas
Process safety management:
Going beyond functional safety
Modern hydrocarbon processing facilities have become
increasingly more complex. Likewise, the risks in managing
greater capacity refineries and petrochemical complexes have
increased. Ensuring the safety of employees, the environment
and physical plant assets in the event of an unexpected process
excursion cannot be overstated. The development of new tech-
niques and technologies designed to improve operational safe-
ty has evolved to meet these challenges. Operating companies
are increasing efforts to reduce the risk of catastrophic events
such as the release of toxic, reactive or explosive chemicals that
can damage the environment or plant assets, as well as, cause
injury or death to employees and the general public.
ROAD TO IMPROVING PLANT SAFETY
This journey begins with the development of the modern
process safety management (PSM) systems and requirements.
Efforts to improve plant safety were led by state-of-the-art
functional safety systems. These systems enable the orderly
shutdown of processing units when abnormal situations occur
that are beyond the capabilities of the regulatory control sys-
tem or operators to correct or to prevent a catastrophe.
While functional safety has proven successful in reducing
the probability of catastrophic events and recognizes the role
of human factors, it does not explicitly address the key roles
of management and business processes in maintaining opera-
tional integrity and profitable performance of process plants.
In this context, what are the approaches that operating compa-
nies should take to go beyond functional safety to proactively
measure, monitor and display a plants risk profile in near real
time so that proper actions can be taken in a more timely man-
ner to improve process safety performance?
Why invest time and resources to go beyond the limita-
tions of functional safety? To answer this question, we must
discuss the pivotal concepts of safety-performance indicators
and values (plant assets, the environment, the public and em-
ployees) at risk from potential catastrophic events. What are
the best practices for establishing a PSM culture along with
designing, implementing and maintaining a proactive PSM sys-
tem to complement existing functional safety systems?
HISTORY OF SAFETY MANAGEMENT SYSTEMS
As industrialization and technology progressed in the early
20th century, the pattern of intermittent catastrophes began.
In 1921, at the BASF plant in Oppau, Germany, explosions
destroyed the plant, killing at least 430 people and damaging
approximately 700 houses nearby. This explosion occurred
as blasting powder was used to breakup the storage pile of a
50/50 mixture of ammonium sulfate and ammonium nitrate.
This procedure had previously been used 16,000 times without
any mishap. In 1947, a fire and explosion in Texas City, Texas,
on the Monsanto Chemical Co.s S.S. Grandcamp while loading
ammonium nitrate fertilizer killed over 430 people. There was
no specific legislative response to these incidents.
1
Interestingly, the US Center for Chemical Process Safety
(CCPS), which provides leadership and infrastructure to pro-
mote and advance PSM, suggests process safety was born on
the banks of the Brandywine River in the early days of the 19th
century at E. I. du Ponts black powder works. Recognizing
that even a small incident could precipitate considerable dam-
age and loss of life, du Pont directed the works to be built and
operated under very specific safety conditions.
2
Industry has a
short memory; here is a brief list of several recent major indus-
trial disasters with dire consequences:
1984Bhopal, India. A toxic material released caused 2,500
immediate fatalities and many other offsite injuries over time.
1984Mexico City, Mexico. An LPG explosion caused
300 fatalities (mostly offsite) along with $20 million in damages.
1988Norco, Louisiana. A hydrocarbon-vapor-cloud ex-
plosion resulted in seven onsite fatalities and 42 injuries, as well
as over $400 million in damages.
1989Pasadena, Texas. An ethylene/isobutene explo-
sion and fire caused 23 fatalities, 130 injuries and more than
$800 million in damages.
Such catastrophic safety incidents damaged the public and
the environment. They also caused significant economic loss. In
response, governments continue to enact legislation and impose
fines focused on reducing the probability of future events. Like-
wise, operating companies formed safety-related consortiums
that include suppliers of process automation technology. The
goal is to identify automation solutions that can enable operat-
ing companies to avoid catastrophic safety events through early
detection and correction. As evidenced by recent safety-related
catastrophes, such solutions have not been entirely successful.
The present state-of-the-art safety management includes
safety studies (HAZID, HAZOP, risk analysis), safety instru-
mented systems (SISs) for fire and gas detection, and emergen-
cy shutdown, abnormal situation management applications,
and operator guidance tools. As illustrated in FIG. 1, the first
Safety Developments
step in implementing a functional safety system is the upfront
analysis and conceptual design. It begins with a meeting with
all stakeholders to determine possible hazards and hazard char-
acteristics, and to establish the basic scope of the project. Work
then proceeds to develop the detailed design for the SIS. The
next steps involve:
Executing the process hazard analysis (PHA) and layers
of protection analysis (LOPA)
Specifying the safety instrumented functions (SIFs) and
preparing the safety requirements specification (SRS) reports
Developing the safety integrity level (SIL) verification
worksheet and report.
While these approaches to safety management have pro-
duced positive results in reducing the probability of potentially
dangerous process upsets or failures, they are either static (e.g.,
HAZOP studies) or reactive (e.g., emergency shutdown sys-
tems) in nature. Their performance is also hampered by com-
placency. Time passing without an incident is not necessarily
an indication that all is well. There is always a succession of
failings that lead to an incident, as shown by the Swiss-cheese
model (FIG. 2). If unchecked, all systems will deteriorate over
time, and major incidents can occur when defects cross a num-
ber of risk-control systems concurrently. In effect, the holes
in the Swiss-cheese model become larger. Without setting
leading and lagging indicators for each risk-critical control sys-
tem, it is unlikely that failings in these barriers will be revealed
as they arise before all of the important barriers are defeated.
Numerous recent high-profile incidents have heightened
the awareness that organizations need to pay more attention
to process safety. By definition, process safety is a blending
of engineering and management skills focused on preventing
catastrophic accidents and near hitsparticularly, explosions,
fires and damaging releases associated with the loss of contain-
ment of energy or dangerous substances such as chemicals and
petroleum products.
These engineering and management skills exceed those
required for managing the workplace. As industrial infrastruc-
tures continue to age, the consequences of applying process
safety incorrectly increases with escalating consequences, such
as:
Damage to people, the community and environment
Litigation against corporations and individuals
Increased scrutiny by regulators and governments
Undermined investor confidence with resulting loss in
stock price.
In some cases, even when executives and managers have
prioritized process safety, things still go wrong. Too often, or-
ganizations or individuals make process-safety decisions under
pressure, or without proper context or sufficient information.
Whats missing is the ability to provide plant personnel with
real-time, proactive actionable information about the plants
risk profile via continuous measurement, monitoring and vi-
sualization of key operating and safety-related parameters.
Result: Potentially hazardous events can be averted without
resorting to a plant trip or an emergency shutdown. This is the
goal of PSM; it involves next-generation automation solutions
aimed at making step-change improvements in safety perfor-
mance. Such systems can provide a safety early warning and
hazard avoidance system. This should be an essential compo-
nent of the modern hydrocarbon enterprise.
By way of definition, PSM is the application of management
systems to identify, understand and control process hazards,
thus preventing process-related injuries and incidents.
3
The
goal is to minimize process incidents by evaluating the whole
process. PSM came into widespread use after the adoption of
OSHA Standard 29 CFR 1910.119 Process Safety Management
of Highly Hazardous Chemicals in 1992. PSM covers:
Process safety information
Employee involvement
PHAs
Operating procedures
Training
Contractors
Pre-startup safety reviews
Mechanical integrity
Hot work
Management of change
Develop conceptual
process design
basic project scope
SIS safety lifecycle Upfront activity (analysis, conceptual)
Basic project scope
Process characteristics
Process details
Process ow diagram
Identify
PHA potential SIF
Typical process history
Possible hazards
Hazards characteristics
P&ID (rough)
Execute
consequence analysis
LOPA
Hazards classication
Consequence matrix
Tolerable frequency
Initiating events
Enable factors
Probability of exposure
Failure probabilities
IPL credits
Risk reductions
PHA report
LOPA report
Develop safety
function requirements
Corporate SIS standards
International standards
Prescriptive subsystems
SIS operation
requirements
SIS maintenance
requirements
P&ID (seminal)
FDS, SIF matrix
SRS
Safety lifecycle chart
SIF dossier
Develop SIS
conceptual design
SIS detail design
Non-SIS detail design
Perform
SIL verication
Develop non-SIS
conceptual design
SIF, Non-SIF functions
C&E charts
SIS interlocks requirements
SIS hardware concept
SIS operator interface
SIL verication report
SIL verication worksheet
FIG. 1. Steps in the FEED of a safety instrumented system.
Hazard
Accident
SIS
DCS
Other
Process design
FIG. 2. Swiss-cheese model of how a hazard can propagate and
become a harmful event.
Safety Developments
Incident investigation
Emergency planning and response
Compliance audits
Trade secrets.
Another definition of PSM is the proactive and system-
atic identification, evaluation and mitigation or prevention of
chemical releases that could occur as a result of failures in pro-
cesses, procedures or equipment.
4
PSM is intended
to ensure freedom from unacceptable risk due to:
Fire
Explosion
Suffocation
Poisoning.
FIG. 3 shows where PSM fits into the overall con-
text of operational integrity (i.e., keeping the process
in the pipe), and how functional safety is a key ele-
ment of PSM.
Business case for PSM. A cost/benefit analysis
is at the center of decision-making on investments. To justify
cost, it is necessary to determine if the magnitude of the value
delivered justifies the cost in terms of time, effort and money.
Investments in safetyfunctional safety systems, abnormal
situation management applications, etc.have been made
largely to satisfy legislative requirements and to maintain the
license to operate. There is no legislation that directly defines
the requirements for a real-time PSM system or the penalties
for not implementing one. Thus, investments in a PSM system
may be made if it can be shown that it delivers a significant,
tangible reduction in the risk of a catastrophic failure, and that
it produces a measurable economic benefit for the plant. TABLE
1 summarizes estimated annual benefits associated with imple-
menting a PSM system. For a 100,000-bpd petroleum refinery,
operating for 330 days/yr at an average refining margin of $5/
bbl, the estimated annual PSM benefit is $2.85 million. In ad-
dition to the stated benefits from TABLE 1, the incremental
value-at-risk can provide ongoing quantified measures of the
economic impact from the PSM system.
DESIGN AND FRAMEWORK FOR A PSM SYSTEM
It is important to find the right level of balance among the
various possible safety indicators so that process-safety deci-
sions accurately reflect the companys desired operational risk
profile. Although risk can never be eliminated, a variety of
mechanisms can be put in place to balance desired safety out-
comes with day-to-day business imperatives and pressures.
Too often, many organizations rely heavily on failure data
to monitor performance. Thus, improvements or changes are
only determined after something has gone wrong. Often, the
difference between whether a system failure results in a minor
or catastrophic outcome is purely down to chance. The conse-
quence of this approach is that improvements or changes are
only determined after something has gone wrong. Discovering
weaknesses in the quality of managing the process and control
systems by having a major incident is too late and costly. Early
warning of dangerous deterioration within critical systems pro-
vides an opportunity to avoid major incidents.
Knowing that process risks are successfully controlled has a
clear link with business efficiency, as several indicators can be
used to show plant availability and optimizes operating condi-
tions. Effective management of major hazards requires a proac-
tive approach to risk management. Information to confirm that
critical systems are operating as intended is essential. Leading
indicators that can confirm that risk controls are contining to
operate is an important step forward in the management of ma-
jor hazard risks.
Measuring performance. The main reason for measuring pro-
cess safety performance is to provide ongoing assurance that risks
are being adequately controlled. Directors and senior managers
need to monitor the effectiveness of internal controls against
business risks. For petroleum refineries and petro chemical man-
ufacturers, process safety risks are a significant aspect of busi-
ness risk, asset integrity and reputation. Many organizations lack
good information to show how well they are managing major
hazard risks. This is because the information gathered tends to
be limited to measuring failures, such as incidents or near misses.
Those involved in managing process safety risks need to ask
fundamental questions about their systems, such as:
What can go wrong?
What controls are in place to prevent major incidents?
What does each control deliver in terms of a safety out-
come?
How do we know that the controls continue to operate
as intended?
Measuring performance before a catastrophic failure.
According to James Reason, (major) accidents result when
a series of failings within several critical risk-control systems
materialize concurrently.
5
Each risk-control system represents
an important barrier or safeguard within the PSM system. A
Keeping the process in the pipe
Operational integrity
Process safety
|ec|e
|rcte::e:
|a|ner|:{:|en:
Occupational safety
Ir|:
\||:
|||:
Functional safety
|C\
\|\
k|rn:
FIG. 3. Role of PSM in supporting operational integrity.
Since the advent of the modern
hydrocarbon age, petroleum refining and
petrochemical process operations have
become increasingly complex and potentially
very dangerous if not managed correctly.
Safety Developments
significant failing in just one critical barrier may be sufficient
to give rise to a major accident. Continuously measuring and
monitoring the actual real-time performance of these safety
barriers ensures that operational integrity is not compromised
due to degradation of barriers.
Leading and lagging indicators are set in a structured and
systematic way for each critical risk-control system within the
whole PSM system. In tandem, they act as system guardians,
providing dual assurance to confirm that the risk-control sys-
tem is operating as intended or providing a warning that prob-
lems are starting to develop.
Leading indicators are an active monitoring form focused
on a few critical risk-control systems to ensure continued effec-
tiveness. Leading indicators require a routine systematic check
that key actions or activities are undertaken as intended. They
can be considered as measures of process or inputs essential to
deliver the desired safety outcome. The leading indicators iden-
tify failings or holes in vital aspects discovered during routine
checks on the operation of a critical activity within the risk-
control system.
Lagging indicators are reactive monitoring methods re-
quiring the reporting and investigation of specific incidents
and events to discover weaknesses within that system. These
incidents or events do not have to result in major damage or
injury or even loss of containment, providing they represent
a failure of a significant control system that guards against or
limits the consequences of a major incident. Lagging indicators
show when a desired safety outcome has failed or has not been
achieved. The lagging indicator reveals failings or holes in
that barrier discovered following an incident or adverse event.
The incident does not necessarily have to result in injury or
environmental damage, and it can be a near miss, a precursor
event or an undesired outcome attributable to a failing in that
risk-control system.
Several organizations and standards recommend applying
leading and lagging metrics to understand the quality of the
PSM system. Several examples are:
ISA 84.00.04Recommended Practices for Guidelines for the
Implementation of ANSI/ISA-84.00.01-2004 (IEC 61511 Mod)
CCPS
TABLE 1. Operator training simulator potential benets
Potential PSM benets
Assumptions Value estimates
Maximum sustainable daily rate (bpd) = 100,000
Margin ($/bbl) = $5
Notes Potential, $
Annual
probability, %
Actual
cash, $ Benet type
Loss avoidance
1. Catastrophic loss $39,860 4% $1,594
Human life 1 death + 5 serious injuries $20,000
Cleanup $660
Compensation to local businesses $200
Fines Punitive environmental ne $1,000
Equipment replacement 1 heater destroyed
Damage to 2 adjacent heaters
Damage to reactor
Catalyst losses
$4,000
Loss of earnings 20,000 BPD of gasoline for 3 months $9,000
2. Reputation $7,513 4% $301
Loss of sales 5% of 70,000 bpd of fuel sales for 1 year $6,388
Hiring and retaining staf 3% Loss of total staf of 1,500 employees;
Hiring Cost = $25,000/new employee
$1,125
3. License to operate $3,190 4% $128
Safety Additional sensors and safeguards; updated
HAZOP; revised ESD logic; additonal bunding
$2,690
Environmental Automated reporting system $500
Loss avoidance subtotal $50,563 $2,023
Improved economic performance
Productivity benets 0.5% increase in output due to: $825 100% $825
Shorter startups
Fewer unplanned shutdowns
Faster grade/throughput changes
Better handling of process disturbances
Direct cash benets $51,388 $2,848
Safety Developments
The Energy Institute (EI), formerly known as the Petro-
leum Institute.
The common theme of these metrics is applying key per-
formance indicators (KPIs) generated from the management
of the process/functional safety equipment and the people and
processes that are used in terms of their competence, leader-
ship and risk-management capabilities.
For example, the EI has published a Process Safety Manage-
ment framework, developed by the energy industry, for use by
various industry sectors.
6
The framework is intended to be ap-
plicable worldwide, to all process industries such as power, pe-
troleum, chemicals, refining, etc. The framework encapsulates
learning from people with practical experience of developing
and implementing PSM as part of an integrated management
system. It clearly sets out what needs to be done to ensure the
integrity of the operation and define what measures should be
in place and how they are performing. Note: It is not intended
to replace existing process safety or health, safety and environ-
mental (HSE) management systems.
The EIs framework consists of three levels: focus areas, ele-
ments and expectations. The focus areas set out the high-level
components of the PSM framework. Within each of the focus
areas are a number of elements. Each element contains expec-
tations defining what organizations need to do properly to
meet the intent of each element. Details for EIs PSM elements
set four key operating aspects that organizations should do to
ensure the integrity of the operations:
Process safety leadership
0 Leadership commitment and responsibility
0 Identification and compliance with legislation and in-
dustry standards
0 Employee selection, placement, competency and health
assurance
0 Workforce involvement
0 Communication with stakeholders
Risk identification and assessment
0 Hazard identification and risk assessment
0 Documentation, records and knowledge management
Risk management
0 Operating manuals and procedures
0 Process and operational status monitoring, and handover
0 Management of operational interfaces
0 Standards and practices
0 Management of change and project management
0 Operational readiness and process startup
0 Emergency preparedness
0 Inspection and maintenance
0 Management of safety-critical devices
0 Work control, permit to work and task risk management
0 Contractor and supplier, selection and management
Review and improvement
0 Incident reporting and investigation
0 Audit, assurance, management review and intervention.
FIG. 4 shows the proposed PSM frameworkbased on in-
dustry guidelinesand the associated components of a well-
designed PSM system to enable real-time measurement and
monitoring of a plants risk profile. It provides actionable infor-
Customer
self assessment
Solution
design
Corporate and
site management
Operations,
maintenance and
engineering
Dashboards
leading and lagging KPIs
Safety performance
indicator calc. engine
Industry
guidelines
Integrated information
and workow platform
PSM support
applications/solutions
Solution
implementation
S
e
r
v
i
c
e
s
S
o
f
t
w
a
r
e
P
S
M

f
r
a
m
e
w
o
r
k
FIG. 4. PSM framework and components.
Complacency
Process
plant
PSM
Key
performance
Designed risk
+
FIG. 5. PSM control loop.

Plant
SPI
Asset risk
LOE
KPI
Asset risk
LOPs
KPIs
FIG. 7. Plant-safety model with KPIs and SPI.
Plant 1
KPI framework
LOE 1
LOP LOP LOP LOP LOPs
LOE 2
Plant 2 Plant 3
FIG. 6. Asset-owner safety model.
Safety Developments
mation that can be used to prevent catastrophic events. Where
an organization has an existing HSE or PSM system, it may be
useful to benchmark against the framework or to carry out a
risk assessment vs. the expectations of each element and identi-
fy any aspects of the existing system that may need enhancing.
Implementing such a PSM system establishes the founda-
tion of a PSM control loop. FIG. 5 illustrates such a control
loop to prevent complacency from increasing the probability
of a catastrophic event due to plant personnel ignoring leading
and lagging indicators about degradation of protection levels
provided by risk-control loops.
During plant operations, systems are modified to adapt to
the changing system needs. Systems and procedures can deteri-
orate over time, and system failures discovered following a ma-
jor incident frequently surprise senior managers, who sincerely
believed that the controls were functioning as designed. Used
effectively, process safety KPIs can provide an early warning
that critical controls have deteriorated to an unacceptable level.
Measuring performance to assess how effectively risks are
being controlled is an essential part of an HSE system. This can
be accomplished in two ways:
Active monitoring. It provides feedback on perfor-
mance before an accident or incident
Reactive monitoring. It involves identifying and re-
porting on incidents to check that the controls in place are ad-
equate, to identify weaknesses or gaps in control systems and
to learn from mistakes.
SPIs and incremental value-at-risk. After a set of KPIs
have been adopted, the asset owners management is respon-
sible for monitoring these KPIs and responding to deviations
from their baselines. At higher management levels, the rel-
evance of the KPIs associated with managing plant equipment
can be lost. Therefore, it becomes necessary to translate the
individual equipment level KPIs and their business impact into
plant-level safety performance indicators and its business im-
pact. This concept can be extended to any number of facilities
enabling upper management to understand the quality of PSM
across the enterprise.
Using the individual equipment KPIs, a new approach allows
an asset owner to understand the overall safety state of the plant
and its economic impact on the business. In addition, this ap-
proach is tied to the existing LOPA and financial impact analysis.
KPI metrics are gathered based on the asset owners manage-
ment of the plant equipment, capability of employees and pro-
cesses followed to manage process safety. Typically, 1020 key
metrics can be covered and include 1) management of safety-re-
lated equipment (e.g., completion of periodic field-device proof
tests associated with a distillation column), 2) competence of
plant personnel (e.g., their level of training and skills testing),
3) adherence to established procedures (e.g., near-miss inves-
tigations) and 4) leadership (e.g., involvement of leadership in
periodic, formal safety reviews). These metrics can originate
from management based on the layers of protection (LOPs) as-
sociated with the different lines of equipment, from at a LOP
level (e.g., SIS) or at the line of equipment level (leadership).
The safety performance indicator (SPI) is an aggregation of
the individual KPIs into a single number.
The SPI can be calculated at the equip-
ment level (equipment SPI) and at the
plant level. FIG. 6 illustrates the owner
safety model for an enterprises global
assets. This model can consist of plants
distributed over different geographic re-
gions. A plant is decomposed into lines
of equipment (LOE), which have LOPs
associated with the plant-safety model, as
shown in FIG. 7.
Underlying the plant-safety model is a
safety related KPI framework; it addresses
the management of process safety related
to plant equipment, business processes,
and procedures used to manage the equip-
ment and the capabilities of employees
applying these processes and procedures.
Corporate
value at risk, $ million
15.1 49.5 4.95
Plant SPI
Inc. asset
at risk,
$ million
Inc. prod.
at risk,
thousand bpd
Inc. prod.
at risk,
$ million
NA-P1 89% 10 30 3
NA-P2 90% 3 10 1
EU-P3 96% 0.1 1 0.1
ME-P4 90% 2 8 0.8
AP-P5 100% 0 0.5 0.05
FIG. 8. Example of a corporate dashboard.
0
Jan Feb Mar Apr MayJuneJuly Aug Sept Oct Nov Dec
20
40
60
80
100
P
e
r
c
e
n
t
0
20
40
60
80
100
P
e
r
c
e
n
t
0
20
40
60
80
100
P
e
r
c
e
n
t
0
20
40
60
80
100
P
e
r
c
e
n
t
0
20
40
60
80
100
P
e
r
c
e
n
t
Leadership Competency
Plant value
at risk
Safety device management Incident reporting
Op. readiness
Inc. rev.
at risk
$ 1 million
Safety performance
indicator
89%
Inc. prod.
at risk
5,000
Inc. asset
at risk
$ 10 million
FIG. 9. Example of a plant-level dashboard.
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Challenge us today
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Safety Developments
Calculating the weighted KPI for a protection layer.
The KPI for a LOP can be calculated as:
KPI _LOP
j
=
e
(w
i
KPI
i
)
i
K
j
e
(w
i
)
i
K
where:
KPI_LOP = Weighted average KPI of a layer of protection
w = Weight of a KPI
7
KPI = Key performance indicator related to plant, process,
people (as applicable)
K = Number of KPIs for an LOP
I = Index for counting number of KPIs
J = Index for counting number of LOPs.
Calculating safety performance index for equipment.
Consider that a piece of equipment has a number of LOPs.
From a safety perspective, the LOPs are of different impor-
tance and risk levels. From the LOPA, each layer has an associ-
ated risk-reduction factor. The weighted KPIs associated with
the equipment can be aggregated and weighted, using the risk-
reduction factor associated with the LOP:
SPI _EQUIP
j
=
w_lop
i
i
L
j
KPI _LOP
i
w
i
i
L
=
rrf
i
KPI _LOP
i
i
L
j
w
i
i
L
where:
L = Number of layers of protection
w_lop = Weight of a layer of protection (= RRF for the layer
of protection)
I = Index for counting LOP
J = Index for counting number of pieces of equipment.
Calculating safety performance index for a facility.
Consider that a facility has a number of LOEs. From a safety
perspective, LOEs are of different importance/risk levels.
From the LOPA, each LOE has associated with it a total equip-
ment risk. The SPIs for the LOEs can be aggregated using the
total risk factor calculated from the LOPA:
SPI _ PLANT=
1
EQ _RISK
i
i
E
SPI _EQUIP
i
1
EQ _RISK
i
i
E
where:
E = Number of pieces of equipment in a plant
I = Index used to count the pieces of equipment in the plant
EQ_RISK = Total mitigated risk for a piece of equipment
8
SPI_PLANT = SPI for the plant
Estimated losses associated with LOE risk and plant.
Based on the SPI, a safety performance state can be calculated.
For example, the SPI can have ranges such as good (> 95%),
warning (90% to 95%) and bad (< 90%). Associated with
each LOE is an asset impact. For example, the asset impact
may be defined as S0 to S5, as shown in TABLE 2. Incremental
estimated asset value-at-risk is a safety performance adjusted
metric (expected value) that can be calculated using the SPI,
the safety performance state and the asset impact.
For example, the incremental asset value-at-risk can be es-
timated as follows: 100% of the asset loss value-at-risk if the
safety performance state is determined to be bad; 50% of the
asset loss value-at-risk if the safety performance state is deter-
mined to be warning; 0% of the asset loss value-at-risk if the
safety performance state is determined to be good:
LOE: Estimated incremental asset value-at-risk:
=
0 if SPI > 9 5%
0.5 defined asset impact if SPI 90% and 95%
1 defined asset impact if SPI < 90%
The plant-level incremental asset value-at-risk can be estimated
by adding the estimated incremental asset values-at-risk for the
LOEs with the facility. The plant-level incremental production
value-at-risk can be estimated by adding the incremental pro-
duction values-at-risk for the underlying lines of equipment:
Plant: Estimated incremental asset value-at-risk:
= LOE incremental asset value-at-risk
Plant: Esimated incremental production capacity at risk:

=
0 if Plant SPI > 95%
0.5defined production capacity if Plant SPI 90%
and 95%
1defined production capacity if Plant SPI < 90%
For a corporation with many plants, the incremental asset val-

ues-at-risk and the product values-at-risk can be aggregated as:
Corporation: Estimated incremental Asset value-at-risk:
= Plant incremental asset value at risk
Corporation: Estimated incremental production capacity at risk:
= Plant incremental asset value-at-risk
Dashboards. To display the SPI and related incremental asset
value-at-risk and incremental production loss, dashboards can
be used, as shown in FIGS. 8 and 9. The plant-level dashboard
could display the plant safety-performance data and provide
drill-down capability to the underlying KPIs for analysis of the
underlying causes of identified risks. Once identified, correc-
tive action plans can be defined and implemented in a timely
manner to avoid costly catastrophic safety events.
TABLE 2. Asset impact levels vs. asset value and production losses
Level Asset loss value Production loss, bbl
S0 $10,000 0
S1 $100,000 1,000
S2 $1,000,000 5,000
S3 $10,000,000 15,000
S4 $100,000,000 50,000
S5 $1,000,000,000 100,000
Safety Developments
Best practices and lessons learned. As proven with the
name of the American Fuel and Petrochemical Manufacturers
(AFPMs) safety conference, i.e., the National Occupational
and Process Safety Conference, the refining and petrochemi-
cal industries are clearly focused on PSM as a key component
of their operational strategies. To support these operational
strategies, there are nine steps or best practices to use when
implementing and maintaining an effective process safety-
performance management system:
Step 1. Establish the organizational arrangements/rela-
tionships needed to implement indicators.
Step 2. Decide on the scope of the indicators.
Step 3. Identify the risk-control systems and decide on the
outcomes.
Step 4. Identify critical elements of each risk-control system.
Step 5. Establish the data collection and reporting system.
Step 6. Review (benchmark against the IE PSM Frame-
work or equivalent).
Step 7. Deploy the KPI model and SPI calculations.
Step 8. Educate management on the importance of PSM.
Step 9. Establish management roles and actions for review
of KPIs, SPIs, estimated asset value-at-risk and estimated pro-
duction value-at-risk.
LITERATURE CITED
1
A Canadian Perspective of the History of Process Safety Management Legislation,
8th International Symposium: Programmable Electronic System in Safety-Related
Applications, Sept. 23, 2008, Cologne, Germany.
2
Center for Chemical Process Safety website: http://www.aiche.org/CCPS/
Students/GetSmart.aspx.
3
Center for Chemical Process Safety website: http://www.aiche.org/CCPS/
Students/GetSmart.aspx.
4
H. J. Toups, LSU Department of Chemical Engineering, with significant material
from SACHE 2003 Workshop.
5
Managing the Risks of Organizational Accidents, Ashgate Publishing Co., 1997.
6
Energy Institute, London, 1st Ed., December 2010.
7
A weight of 0 signifies that a KPI is not used.
8
This is equal to the sum of all the mitigated risks for an item of equipment.
MARTIN A. TURK, PhD is the director of Global Industry
Solutions for the HPI for Invensys Operations Management at
Houston, Texas. For most of his 40+ years of experience, Dr. Turk
has been involved in engineering, consulting, sales and
marketing activities related to process automation. These
activities include process simulation, advanced control and
information/automation system strategic planning. Dr. Turk is
responsible for definition of industry-specific solutions for downstream petroleum
refining and petrochemicals, participation in industry conferences and working
with Invensys clients worldwide to identify and quantify automation opportunities
in their manufacturing facilities that will provide them with significant returns on
investments. He received his BS degree in chemical engineering from the University
of Dayton and his PhD in chemical engineering from the University of Notre Dame.
Also, he has published technical papers and made presentations at domestic and
international seminars on a variety of subjects related to advanced automation
solutions for the process industries.
AJAY MISHRA is the R&D program manager at Invensys. He
helps define the detailed features and technology roadmaps
for the Triconex branded safety & critical control products. Mr.
Mishra holds a BSEE degree from the College of Engineering,
Pune, India and an MBA from the UCLA Anderson School of
Management. He has over 20 years of experience in safety and
critical control systems in process control SIS, and railways
systems including product development, project engineering, project
management and product management. Mr. Mishra is a TV certified Functional
Safety Engineer for hardware/software design (IEC 61508) and Safety
Instrumented Systems (IEC 61511).
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Bonus Report
Safety Developments
R. LIMAYE, Praxair, Houston, Texas
Operator response to alarms is an important
protection layer
Operator response to alarms is important layers of protec-
tion (LOP). When implemented with good design, engineering
and maintenance practices, an alarm can help reduce the safety
integrity level (SIL) of a safety instrumented function (SIF).
The ISA84 standard covers the functional safety life cycle
requirements of safety instrumented systems (SISs) and has
been recognized by the US Occupational Safety and Hazard
Administration (OSHA) as a generally accepted good engi-
neering practice that can be used to comply with the process
safety management (PSM) standard 29CFR1910.119 for SIS.
In the initial phase of the safety life cycle, hazard and risk assess-
ments identify the risks associated with the process. The risk is
reduced to a tolerable level as defined by the corporate standard
by implementing safety functions that act as LOP.
Layers of protection analysis (LOPA) is the most commonly
used technique in the process industry, especially for selecting
the amount of risk reduction required to be provided by each
protection layer. If the risk is not reduced to a tolerable level us-
ing non-instrumented safety functions such as pressure safety
valves (PSVs), mechanical stops and process design, then ad-
ditional risk reduction is necessary by means of a SIF imple-
mented in a SIS. Often, the performance requirement of a SIF
can be reduced by one order of magnitude by implementing an
operator response to an alarm as a protection layer. Reducing
SIL requirements (e.g., from SIL3 to SIL2) offers huge capital
and maintenance cost savings. The higher the SIL, the higher
the cost of implementation and maintenance.
The ISA18.2 standard describes the alarm management
life cycle. However, the standard does not give enough guid-
ance on the alarms that have been credited in LOPA for risk
reduction. The standard talks about the alarm classification
and defines highly managed alarms as a special class that has
requirements similar to the alarm for which credit has been
taken in LOPA for risk reduction. The rules for taking credit
for an operator response to an alarm are defined in the ISA84
standard. Teams performing alarm engineering may not have
familiarity with the requirements of ISA84; therefore, those re-
quirements are outlined here. If alarm management and func-
tional safety teams come up with separate lists and databases, it
becomes difficult for operations to maintain and keep the lists
up-to-date. The best practices for maintaining a common list as
a master alarm database will be discussed here.
The ISA 18.2 alarm management standard provides a life
cycle approach to manage alarms starting from alarm phi-
losophy and rationalization to operations and maintenance.
It states the mandatory and nonmandatory requirements for
alarm engineering in different stages of the life cycle. The stan-
dard refers to ISA84 for the requirements of alarms related to
process safety. In many organizations, the teams who perform
the alarm management life cycle steps are different from those
who work on SISs and may not be familiar to the requirements
of ISA84, which imposes specific requirements on the alarms
related to process safety. The LOP model identifies the process
alarm as one of the protection layers in reducing the demand
rate on SISs. Although casual verbal or written communication
refers to alarms as a protection layer, the correct term is opera-
tor response to alarm as protection layer.
LOPA. To illustrate the concept, consider a process example
consisting of a high-pressure (HP) knockout drum, as shown
in FIG. 1. The product gas at high pressure and temperature exit-
ing the reformer is cooled in a process gas cooler, which con-
denses the water in the gas. The condensate is removed in the
knockout drum V-100. The liquid level in the knockout drum is
controlled by a level control loop, LC-100. The normal operat-
ing range of 35%50% has been established to maintain a liquid
level blanket in the knockout drum. If the level goes high, the
LT
100A
LC
100
LP storage tank
LT
100C
LT
100B
LAL
100
SIF
1
SP
PV
OP
LALL
100
50
35
30
10
Normal
operating
range
Low alarm
Low level trip
Product gas
HP
product gas +
condensate
Knockout drum
Regulating valve
LV-100
On/of valve
XV-100
V-100
V-101
FIG. 1. An example of the knockout drum process.
Safety Developments
separation will not occur, as the liquid will be carried over into
the product stream. If the level drops too low, there is a risk of
the HP gas entering the low-pressure (LP) system downstream
of the control valve LV-100. Maintaining the liquid level blanket
to avoid this hazardous event is very important.
The low alarm limit for the pre-trip safety-related alarm is set
to 30%. A SIF is implemented to prevent the HP gas from enter-
ing the LP system. If the level falls below the trip limit of 10%,
then the on-off valve XV-100 closes.
During hazard and risk assessments, all possible process risk
scenarios are identified and documented. Hazard and oper-
ability (HAZOP) studies are one of the most commonly used
techniques of performing process hazard assessments. The
scenarios are risk ranked based on the risk matrix developed
by the organization. The risk matrix typically defines different
levels depending on the severity of consequence and likelihood
of the hazardous event. The scenarios with risks higher than a
predefined threshold level are considered for LOPA to ensure
adequate LOP exist. For the process scenario described previ-
ously, an extract from the LOPA is presented in TABLE 1. The
safety functions are assigned to LOP during LOPA.
Two independent protection layers are identified in the
LOPA example above. The first protection layer is the operator
response to an alarm with a risk reduction factor (RRF) of 10.
The RRF is also represented in terms of probability of failure
on demand (PFD
avg
). In this instance, PFD
avg
= 1/RRF = 1 X
10-1. As per ISA84, the maximum risk reduction that can be as-
signed to operator response to an alarm implemented in a basic
process control system (BPCS) is 10.
The second protection layer is a SIF with an RRF greater
than 100. A SIF is a combination of sensor, logic solver and final
control element. The logic solver is often referred to as the SIS.
The logic of a SIF is executed in the SIS. The amount of risk
reduction provided by the SIF determines the SIL of the SIF.
As shown in TABLE 2, there are four SILs defined in the ISA84
standard that offer different bands of risk reduction.
In the LOPA example, the SIF must offer an RRF of greater
than 100 to reduce the overall PFD
avg
to less than 1x10
5
and
thus the SIF has a SIL requirement of SIL2. Without the alarm,
the SIF must have an RRF greater than 1,000 (or PFD
avg
< 1 X
10
3
), making it a SIL3 SIF. A SIL3 SIF requires considerably
higher capital cost to implement. For example, it may require
two ON/OFF valves in a double block and bleed arrangement,
an additional pressure transmitter for pressure between the two
block valves and a logic solver with much more stringent re-
quirements of failures rates.
Safety related alarm. An alarm is called a safety related
alarm (SRA) when operator response to the alarm is used as a
protection layer to reduce the overall risk of hazardous process
events. This alarm is identified in LOPA and a risk reduction
credit is taken for the operator response to the alarm. Other
terms used to describe this alarm type are: critical alarm, safe-
ty-critical alarm and process safety alarm. The ISA18.2 stan-
dard talks about an alarm class called highly managed alarms
(HMAs). The ISA84 life cycle requirements of SRA are similar
to those of highly managed alarms, although many people do
not like to use the term highly managed alarms to classify
safety-related alarms.
Considerations for using operator response to an alarm as a
protection layer are summarized as:
The sensor used for the alarm system is not used for con-
trol purposes where loss of control would lead to a demand on
the SIF
The sensor used for the alarm system is not used as part
of the SIS
Limitations have been taken into account with respect to
risk reduction that can be claimed for the BPCS and common
cause issues
Risk reduction claimed is not more than a factor of 10
There is sufficient time for the operator to take corrective
action
Documented description of the response to the alarm
(corrective action) is available, and rationalization has been
performed
The operator has been trained to take preventive actions
Performance shaping factors have been considered
Human ergonomic factors have been considered
The test and maintenance requirements are the same as
any other independent protection layer
TABLE 1. An example of LOPA
Hazard description
Loss of primary containment of the product gas upon failure of level
control. Loss of liquid blanket in KO drum V-100 and HP ammable gas
entering the LP system through KO drum bottom with a possibility of
explosion and fatality.
Description
Probability
(frequency per year)
Tolerable risk (dened by
organization) [ 1 in 100,000]
1 X 10
5
Likelihood of initiating event
(control loop failure) [1 in 10]
1 X 10
1
Probability of ignition 1
Likelihood of operator present
near the vessel
1 X 10
1
Frequency of unmitigated
consequence
1 X 10
2
Independent protection layers
IPL description Probability of failure
IPL-1 Operator response to low alarm
in KO drum
1 X 10
1
IPL-2 SIF to close the valve XV-100 upon
low-low level alarm
1 X 10
2
Frequency of mitigated consequence 1 X 10
5
TABLE 2. SIL determination
SIL
Demand mode
Target PFD
avg
Target RRF
1 > = 10
2
to < 10
1
> 10 to < = 100
2 > = 10
3
to < 10
2
> 100 to < = 1,000
3 > = 10
4
to < 10
3
> 1,000 to < = 10,000
4 > = 10
5
to < 10
4
> 10,000 to < = 100,000
Safety Developments
The sensor used for generating alarms should be tested at
a proof test interval established in the safety requirements speci-
fications
The person who performed the tests and any maintenance
should be documented and archived for the records
Access control: Access to make changes to alarm param-
eters such as alarm setpoint, priority and filter constant are re-
stricted, and the proper management of change (MOC) process
is followed to make any changes once the system is put in service.
Independency requirements. ISA84 clause 11.2.10 states
that one should not share a device with a SIF and control func-
tion where failure of the device will cause the BPCS loop to
place a demand on the SIS and simultaneously cause the SIF
to fail in a dangerous state. Therefore, the same sensor used for
generating an alarm cannot be shared with the control function
in a BPCS and cannot be shared with the SIF implemented in
the SIS. When independent sensors are available for each func-
tion, they can be configured in a fault tolerant mode to achieve
higher reliability and to increase the diagnostic coverage. Each
owner operator company is responsible for doing analysis to en-
sure their configurations are valid and can satisfy the indepen-
dency criteria of ISA84.
Standalone SRA. When the operator response to an alarm is
identified in LOPA as a protection layer, and there are no other
safety instrumented functions or control functions associated
with the measurement, then the transmitter is wired to a BPCS,
as shown in FIG. 2.
SRA and control function. SRAs and control functions are
both implemented in BPCSs. When the same process measure-
ment is required for both the functions, separate transmitters
should be used for alarm and control. Each transmitter should
be wired to separate cards in the controller or preferably separate
controllers of a BPCS.
The two transmitters could be configured in a BPCS, as
shown on the right of FIG. 3, to improve the availability, facili-
tate the maintenance and to improve the diagnostic coverage.
The right side of FIG. 3 also illustrates that a software switch
(HS-100x) is provided for the operator to manually change the
source of input for the alarm, as well as for the control function.
This allows taking one of the transmitters out of service for
maintenance or proof testing. Depending on the functionality
in the BPCS, a deviation alarm should be configured for the
maintenance technician. If the difference between the readings
of two transmitters is more than a pre-set threshold, a low pri-
ority deviation alarm is generated. The operator action for this
alarm is typically to generate the maintenance work order for
the instrument technician to check the transmitters and cor-
rect the situation.
When the hand switch is used to switch the input to another
source, a timer KS-100x should be started with alarm KAH-
100x. If the time in the switched input mode exceeds the pre-
configured limit, an alarm should be generated. The preconfig-
ured timeout limit to generate a warning alarm should be less
than the minimum time to repair (MTTR) of the transmitter. If
the time in the switched state exceeds the MTTR, then the SIF
should initiate the action to put the process in a safe state.
SRAs, control functions and SIFs all need the same process
measurement. When the available instrumentation is adequate
to meet the independency criteria of each function, it is benefi-
cial to wire it in a fault tolerant configuration to improve reliabil-
ity. A typical implementation is shown in FIG. 4. In this example,
the three differential pressure transmitters using independent
taps for process connection are wired to a SIS through the safety
certified current-loop isolator and repeater. The HART trans-
mitters are powered by a SIS and the isolators have the capabil-
ity to pass through the HART signals on each channel.
SIL1 or SIL2 SIF is implemented in a SIS with a 2oo3 voting
logic for the level input signals. Depending on the BPCS, the
actual implementation may differ. FIG. 4 shows a generic repre-
sentation where a middle of 3 selector block is used in a BPCS
that has an SRA configured. Some BPCS have a standard 2oo3
block that can be used as well.
When sharing the transmitters between a BPCS and SIS,
several considerations should be taken into account:
Failure of any hardware or software outside the SIS should
not prevent any SIF from operating correctly
100B
LT
100B
LI
100B
LAL
SRA
FIG. 2. P&ID representation of a stand alone SRA.
100B
LI
100B
LAL
SRA
100A
LT
100
LC
LV-100
100B
LT
100B
LI
100B
LAL
SRA
100A
LT
100
LC
LV-100
100B
HS
100A
HS
100B
KS
100A
KS
100B
KAL
100A
KAL
DEV
100B
LT
FIG. 3. SRA and control functions are both implemented in BPCSs.
100A
LT
100A
LI
100
LAL
SRA
100B
LT
100C
LI
LC-100
100C
LT
XV-100
1
SIF
I
I
I
I
I
I
100
LC
100B
LI
m of 3
m of 3
DEV
100
LALL
LY-100A LY-100B LY-100C
FIG. 4. SRAs, SIFs and control functions are implemented to achieve
high reliability.
Safety Developments
Failure of a BPCS component does not result in the ini-
tiating cause for the process hazard and the failure (or defeat/
bypass) of the SIF that protects against the specific scenario un-
der evaluation
The probability of common mode, common cause or de-
pendent failures has been adequately evaluated and determined
to be sufficiently low; it is often recommended to use diverse
measurement technology to reduce the common cause failure
problems (a combination of differential pressure and guided
wave radar transmitters is an example of using diverse technolo-
gies to measure the same process value)
The shared components are managed according to ISA84,
including proof testing, access security and management of
change
The sensor is powered by the SIS
The signal is transmitted to the BPCS by an optical isolator
or other means to ensure that no failure of the BPCS affects the
functionality of the SIS.
Time considerations. Time available for the operator to take
corrective action is an important factor in alarm engineering.
In the alarm rationalization process, the alarm priority is im-
pacted by the severity of the consequence of inaction to alarms
and the time available for the operator. Alarm philosophy
documents typically recommend the use of a rationalization
matrix of consequence severity and maximum time to respond.
Process safety time (PST) is the difference between the
time at which the unacceptable condition occurs (T
CONDITION
)
and the time where the unwanted event occurs (T
EVENT
).
Process safety time = T
EVENT
T
CONDITION
In the previous example, there are two protection layers.
The process safety time for an alarm is the time when the lev-
el reaches 30% until it goes to the trip setpoint of 10%. The
time can be calculated by dividing the volume of the knock-
out drum for the 20% of instrument range (the difference be-
tween the alarm setpoint and the trip setpoint) by the worst
case flowrate of condensate when the level control valve LV-
100 stays wide open. The process safety time for the SIF can
be calculated in a similar manner. It will be the time when the
level reaches a trip point of 10% until it goes to 0%.
Typically, the process safety time calculation is done by pro-
cess engineers. Such calculations become easy when the process
model is available.
Alarm response time is the difference between the time at
which the alarm condition occurs and the time when the process
starts responding in the direction to correct the alarm condition.
It includes the sensor lag, BPCS lag, operator response time and
any process lag. Process dead time is the amount of time it takes
for the process to begin reacting after corrective action.
Alarm response time = Sensor delay + BPCS delay + Opera-
tor response time + Process dead time
The process safety time for alarm has to be greater than the
alarm response time. These different time elements are shown
in FIG. 5.
Operator response time is impacted by things like human
factors and ergonomics, which are collectively called perfor-
mance shaping factors. As per the ISA18.2 feedback model of
operator process interaction, the operator response time consti-
tutes the following human interactions:
Detect: The operator becomes aware of the deviation from
the desired condition. The design of the alarm system and the
operator interface impact detection of deviation.
Diagnose: The operator uses knowledge and skills to inter-
pret the information and diagnose the situation when determin-
ing the corrective action to take in response.
Respond: The operator takes corrective action in response
to the deviation.
Minimum time to respond is the quickest possible time
to allow an operator to go through the detect, diagnose and re-
spond steps. It should be defined in the alarm philosophy docu-
ment. It is not physically practical to take necessary corrective
actions in less than this time. Three to 10 minutes is the most
commonly used value as a minimum time to respond.
If the required operator response is faster than the minimum
time to respond, then no credit can be taken for the operator
response to alarm as a protection layer. This requirement is ap-
plicable to not just the SRA, but also to any alarm configured
in the system. In such situations, various options should be
reviewed to allow sufficient time for operator response. In the
above process example, the simplest option is to check if a low
alarm setpoint (LAL-100) can be increased to get more process
safety time. Using a restriction orifice to limit the maximum
flow could be another option.
Maximum time to respond is just
what it says, the maximum time available
for an operator to respond. This does not
mean the operator will take this much
time to respond.
Maximum time to respond = Process
safety time for alarm (Process dead time
+ Sensor and BPCS delays)
In most cases, sensor delay and BPCS
delay are very small and could be insignif-
icant. Depending on the application, pro-
cess dead time could also be insignificant.
Therefore:
Maximum time to respond Process
safety time for alarm.
Mean time to respond is the actual
operator response time, somewhere be-
L
e
v
e
l

%
Process safety timealarm Process safety timeSIF
SIF response time
Sensor delay
DCS delay
Alarm
annunciated
Detect
Diagnose
Respond
Process
response
Trip
condition
occurs
Sensor
delay
Read Logic Write
Final control element action
Safe state
Incident
10
0
Time
Note: Not to scale
35-50% Normal operating range
30% Low alarm setpoint
10% Trip setpoint
RL
Alarm
condition
occurs
RL
Operator response Dead time
30
Alarm response time
Process
response
Dead time
FIG. 5. Various time elements in relation to process safety time.
Safety Developments
tween the minimum and maximum time to respond. In FIG. 5,
the operator response time shown represents the mean time to
respond. The detect, diagnose and respond actions shown in the
graph represent the average time for each action.
Alarm rationalization is the process to review potential
alarms, using the principles of the alarm philosophy, to select
alarms for design, and to document the rationale for each alarm.
To determine the alarm priority, the rationalization process typi-
cally uses a matrix of maximum time to respond and the severity
of the consequence of not attending to the alarm.
SIF response time includes the sensor delay, analog input
card scan time, logic execution, writing output to the final con-
trol element and the time it takes for the valve to close. Typical-
ly, valve closing time is most significant in these time elements.
SIF response time should be less than half of the process safety
time for the SIF.
Managing databases. Usually, the functions of alarm manage-
ment, process engineering and SIS engineering are performed
by different individuals or teams in an organization, as each area
requires different competencies and experience. It is important
to have good coordination between these teams. The purpose of
alarm documentation and rationalization is to publish a master
alarm database, which needs to be maintained by operations to
sustain the benefits of alarm engineering efforts done upfront.
Process engineers typically maintain a database of normal
operating limits, safe operating limits, design limits, engineer-
ing unit ranges and the maximum allowable working pressure/
temperature (MAWP, MAWT) for each process measurement.
This database is expected to be maintained throughout the life
of the plant.
The PSM group and SIS engineers identify the safety-relat-
ed alarms during LOPA. These alarms are listed as a protection
layer with a risk reduction credit of up to 10 (PFD
avg
>= 10
1
).
Usually, someone ends up generating a list of SRAs that get
passed on to the operations with an expectation of maintaining
it throughout the life cycle. Managing and maintaining all these
databases can become an overwhelming task for maintenance
and operations organizations. If proper procedures are not in
place, such lists and databases become outdated and the plant
may be out of compliance.
Coordination of these different groups to generate one
single relational database goes a long way in maintaining the
integrity of the information. The solution could be using a sim-
ple homegrown relational database or one of the commercial
software products available in the market. In either case, estab-
lishing the work process that coordinates the effort of different
teams is a key element.
Alarm classification. Alarm classes are used to set common
characteristics and requirements for managing alarms. It is a good
practice to classify all alarms identified in LOPA as safety-related
alarms. It is also recommended to identify these alarms on a
P&ID with SRA written next to the alarm, as shown in FIGS. 24.
In addition to alarms identified in LOPA, the diagnostic alarms
on subsystems involved in SIFs should also be classified as SRAs.
When a dangerous fault is detected in the subsystem (as a
result of diagnostic or proof testing) which can tolerate a sin-
gle hardware fault, the process can continue the safe operation
while the faulty part is being repaired. If the repair of the faulty
part is not completed within the mean time to restoration as-
sumed in the calculation of the probability of random hardware
failure, then a specified action should take place to achieve or
maintain a safe state. When the action involves the operator
notifying maintenance to repair a faulty system in response to
a diagnostic alarm, this diagnostic alarm may be a part of the
BPCS but should be subject to appropriate proof testing and
MOC along with the rest of the SIS.
An alarm can be assigned to multiple classes. The objective
is to create or view different types of lists, using the filters on
alarm classes. The diagnostic alarms could be assigned a class
maintenance related alarm (MRA) in addition to a SRA to in-
dicate it is not a process alarm. ISA18.2 describes highly man-
aged alarms (HMAs) as the classes of alarms that require more
administration and documentation than others. The alarms
identified in LOPA fall in this class. Depending on the alarm
philosophy, the alarms identified in LOPA could be assigned to
both SRA and HMA alarm classes.
Maintenance and documentation. Sensors used for gener-
ating safety-related alarms should be treated as part of the SIS
with respect to the proof test procedures and documentation
required to be maintained as evidence of satisfactory comple-
tion of those procedures. The records that certify proof tests
and inspections were completed require the following as a
minimum of information:
Description of the tests and inspections performed
Dates of the tests and inspections
Name of the person(s) who performed the tests and in-
spections
Unique identifier of the system tested (for example,
tag name, equipment number)
Results of the tests and inspection (for example,
as-found and as-left conditions).
Final thoughts. When operator response to alarm is used as
one of the protection layers to reduce the process risk below a
tolerable level, it is important to pay attention to the require-
ments of the ISA84 standard. The sensor used for generating
an alarm should not be shared with other functions, such as
process control and safety functions. When different functions
need the same process measurement and if multiple sensors are
available to satisfy the independency criteria of each function,
then the sensors should be wired in a fault tolerant configura-
tion to improve the reliability of all the functions.
Another important consideration is to ensure that the opera-
tor response time for the alarm is less than the process safety time.
Coordination of the different teams in an organization to
use and maintain a single relational database for alarm ratio-
nalization, documentation, safety-related alarms and normal
operating limits goes a long way in ensuring the data integrity
for the life of the plant.
RAJEEV LIMAYE is director of control systems and
instrumentation at Praxairs global hydrogen business unit
in Houston, Texas. He has worked in the process automation
industry for over 25 years and holds a PE license in the state
of Texas. Mr. Limaye is a certified functional safety expert and
a member of the ISA84 standards committee.
Bonus Report
Safety Developments
V. RAMNATH, Aker Solutions, Pune, India
Key aspects of design and operational safety
in offsite storage terminals
The Buncefield incident in the UK and the Jaipur fire in
India stand out as major offsite storage terminal disasters in
the European and Asian regions. In the Americas, a similar
explosion rocked the Gulf terminal in San Juan, Puerto Rico,
destroying 22 tanks and forcing the evacuation of hundreds of
nearby residents.
Storage terminal accidents continue to impose considerable
costs in terms of human lives and health, property damage and
public welfare. Multiple segments of the publicparticularly
citizens, citizens groups and the mediaare likely to become
more interested in chemical safety and chemical release risk
reduction once they become aware of the potentially large con-
sequences if proper proceedures are not followed.
On December 11, 2005, at the Hertfordshire oil storage ter-
minal in Buncefield, UK, an unconfined vapor cloud explosion
(UVCE) occurred that eventually overwhelmed 20 large stor-
age tanks (FIG. 1). Fortunately, there were no fatalities; how-
ever, 60 people were injured and there was large-scale damage
and disruption to local businesses and residents.
Recent events. A major accident involving a gasoline vapor
cloud explosion followed by an ignition occurred at Indian
Oils petroleum, oil and lubricants (POL) terminal on October
29, 2009, in Jaipur, India (FIG. 2). Buildings in the immediate
neighborhood were heavily damaged. The effect of this acci-
dent was felt up to 2 km from the site.
Process safety improvement. These incidents highlight the
need for an exhaustive design and safety review of practices
while designing and operating offsite storage terminals to mini-
mize the risk of fatalities and property damage.
Process safety and risk reduction can be effectively achieved
by applying multiple layers of protection (FIG. 3), which are
known in the industry as onion layers. Each protection layer,
when called for, can function independently to prevent or miti-
FIG. 1. Damaged tanks at the Buncefield disaster.
FIG. 2. Fire at the Indian Oil storage terminal in Jaipur, India.
Emergency response
Embankment
Relief devices
SIS
Alarms,
operators
BPCS
Process
Mitigation layers
Prevention layers
FIG. 3. Protection layers.
Safety Developments
gate the undesirable event. These protection layers have the
common goal to control and/or mitigate risk from the facility.
Broadly, these layers, as shown in FIG. 4, can be classified
into prevention and mitigation layers. The objective of the
prevention layers is to reduce the frequency of the undesired
event; whereas, mitigation layers take action in the event of
full or partial failure of the prevention layers.
In the context of storage terminals, several key aspects can
be implemented that play a role in prevention or mitigation of
uncontrolled releases.
Prevention layers. For terminal design, engineers should:
Ensure that the receiving tank has ultimate control of
tank filling, allowing it to safely stop or divert a transfer with-
out depending on the actions of a remote third party
The first body valve on the tank should be a fail and fire
safe remote operated shutoff valve (ROSOV) on the tank noz-
zle inside the dike, operable remotely from outside the dike as
well as from the control room
All other operational valves must be outside the dike area
The piping layout inside the tank dike area should ensure
easy accessibility for any operation
Structural design should be followed to ensure installa-
tion of sleeves to eliminate emissions from slotted guide poles
on floating roof tanks.
Use double seal systems for floating roof tanks where ap-
propriate, based on the nature of the material being stored, the
tank size, throughputs, location considerations and meteorology
Carry out a hazardous operations (HAZOP) study of the
facility during engineering and at decided frequencies during
operation.
Conduct a critical quantitative risk assessment (QRA) of
the facility, which should stress worst case scenarios
Consider fuel storage terminals as hazardous locations
The control room should be located remotely from po-
tential leak sources as is practical; the QRA will de-
termine the blast pressure structural design require-
ments for control rooms
Water tanks and the water pump house should
be located a safe distance from potential leak sources
and the tankage area
Locate buildings and structures in the upwind
direction
Avoid congestion in the storage terminal area,
with the location of individual facilities determined
by the QRA
All buildings not related to terminal operation
should be located outside the plant area, including the
canteen or any other area where sparks and open flames may exist
When a tank storage terminal includes pipeline operations
in the same location, the control rooms for both the tank termi-
nal and pipeline division should be located in the same opera-
tional building
Locate the emergency exit gate away from the main gate
and in a location that is always available for use
Consider radar-level gauges as minimum instrumentation
Leak-detection devices must be installed on the bottom
of all tanks
Install cathodic protection to prevent deterioration of the
tanks through corrosion
To prevent an overflow, tanks should have headspace mar-
gins that enable the filling line to be closed off in time.
For process operations, engineers should:
Develop procedures for periodic testing of overfill pro-
tection
Ensure effective communication within and between op-
erations, maintenance and contractors
Standard operating procedures (SOPs) should be pre-
pared that not only give what the procedures are, but also why
they are needed.
Regular inspections of pipelines, including thickness sur-
veys and pipeline support system analysis should be carried
out and recorded
Closed-circuit television systems should be installed,
covering tank farm areas and other critical areas
Near-miss reporting systems should be in place
Collate incident data on potential failures and operation-
al failures and share the information on risks with the industry.
Develop incident investigation mechanisms for failures
and safety malfunctions.
For basic control systems, engineers should:
The control system needs to have inventory checks to
ensure that the receiving tank has adequate empty volume to
receive material
Setpoints of high-level trips and alarms requiring opera-
tor action should allow sufficient time for action to be taken to
deal with the developing situation.
For alarms, engineers should:
High-level and high-high-level alarms should occur from
independent sensors
Protection layers
Prevention Mitigation
Process
operation
Basic
control
system
SIS
F&G system,
relief system
Bunds/dikes
Emergency
response
Alarms
Terminal
design
FIG. 4. Classifying the layers of protection.
Process safety and risk reduction can be
effectively achieved by employing multiple
layers of protection, which are known in the
industry as onion layers. Each protection
layer can function independently to prevent
or mitigate the undesirable event.
High-level alarms should trigger facility operators to initi-
ate corrective actions, resulting in a shutdown of the pumping
system and isolation of the tank.
For safety instrumented systems (SIS), engineers should:
The overall system for tank filling control should be of
high integrity, with sufficient independence to ensure timely
and safe shutdowns to prevent tank overflow
When changes or modifications to an SIS are planned, the
changes should be subject to a management-of-change process
identifying and addressing any potential safety implications
from the modification
A functional safety assessment should be performed on
each system, typically at the design stage before the system is
commissioned.
Mitigation layers. For fire and gas detection and relief sys-
tems, engineers should:
Review the classification of places where explosive atmo-
spheres may occur and then evaluate the siting and/or protec-
tion of response facilities, such as fire fighting pumps and emer-
gency switch devices
Apply measures to detect hazardous conditions arising
from loss of primary containment
Install gas detectors in bunds
The thermal safety valve should be provided at the operat-
ing manifold (outside of the dike)
Hydrocarbon detectors need to be installed near all poten-
tial leak sources
Install a rim-seal fire detection and protection system in all
floating roof tanks of the terminal
Each facility needs to maintain adequate firefighting
equipment at each pump station and breakout tank area. The
equipment should be plainly marked as firefighting equipment
and located so that it is easily accessible during a fire.
For embankment, engineers should:
Ensure secondary containment, like dikes and bunds, are
constructed from concrete and are leak-proof; the lining re-
quirements must prevent soil or ground contamination
Install systems that prevent or limit the passage of stored
materials via drains to the normal effluent processing route.
For emergency responses, engineers should:
Locate push buttons on motorized valves outside the dike,
where its easily accessible by the operator
Terminal emergency switch devices should be located in
the control room as well as in other strategic locations
Emergency procedures should be written and made avail-
able to all facility personnel, outlining the actions to be taken
during a major incident
Mock drills should include the full shutdown system
activation.
A system should exist to warn neighboring industries of
impending danger and arrangements should be made to enable
their assistance, if necessary.
VINOD RAMNATH works for Aker Solutions process
department in Pune, India. He has experience in the detailed
engineering of process plants, offsite design, quantitative
risk assessment, safety integrity studies and process plant
commissioning/debottlenecking. Mr. Ramnath started his
career with Reliance Industries.
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Optimize feed treatment for polypropylene processes C77
Catalyst news C78
CORPORATE PROFILES
Axens C81 BASF C83 Criterion C85 Grace Catalysts Technologies/Advanced Refining Technologies C87
Haldor Topse C89 Sabin Metal Group of Companies C91 Saint-Gobain NorPro C93
COVER PHOTO
Photos courtesy of Haldor Topse and Sabine Metal.
2013
CATALYST
Special Supplement to
Bulgaria: Cat Tech Services
(South Eastern Europe) Ltd.
Vetrino, 9220, 25
Georgy Rakovski Str.
Phone: +35 9527 46770
Fax: +35 9527 46770
HYDROCARBON PROCESSING|CATALYST 2013 C77
CATALYST
OPTIMIZE FEED TREATMENT FOR
POLYPROPYLENE PROCESS
H. POORKAR, H. SHBRAIN, S. AL-HARBI and A. AL-SAEED, Tasnee, Jubail, Saudi Arabia
Ziegler-Natta catalysts are primarily used in polypropylene
(PP) production. These catalysts are very sensitive to various
poisons and their activity varies according to the nature and
level of catalyst poisons. Among others, typical propylene
polymerization catalyst poisons include acetonitrile, arsine,
carbon dioxide, carbon monoxide (CO), carbonyl sulfide, cy-
clopentadiene, ethylene oxide, oxygen, palladium, phosphine,
moisture, methanol and propylene oxide.
Catalyst poisons usually are present as impurities within
feedstreams like propylene, ethylene and hydrogen. Each of
the poisons has a varying degree of influence on the catalyst
activity. Though their general behavior is known, it is always
difficult to quantify the losses due to individual poisons within
commercial-size plants. Among the difficulties, accurate mea-
surement of trace impurities in ppb levels remains the biggest
challenge. Experience shows that there are great difficulties in
offline sampling as well as online sampling. Changes in pro-
cess conditions during polymerization is also another factor.
It is not always possible to normalize catalyst productivities
against changing process parameters.
CO is one of the strongest poisons for Ziegler-Natta cata-
lysts. If not treated properly at the source unit, CO is present
with the propylene feed as a contaminant and it can reduce
catalyst activity drastically (FIG. 1 and FIG. 2). As per the pub-
lished literature, a concentration of about 6 ppb (wt%) CO
reduces catalyst activity by approximately 5%.
Few PP process technologies specify feed specification as
low as 20 ppb (wt%) in propylene feed to achieve the guaran-
teed figures of catalyst activity. If the feed-treating unit is not
designed carefully to knock down the CO levels to the safe
limit, the facilitys bottom line will shrink due to excessive
catalyst usage and cost.
Commercial examination. This study from a commercially
operating unit shows the importance of using a proper guard
against possible feed contaminants acting as catalyst poisons.
The unit has two different primary sources of propylene supply.
Source A has CO treatment beds (typically, a sulfur removal
bed followed by a CO removal bed) while Source B doesnt
have any guard beds to protect against CO (FIG. 3). Normally
both sources feed propylene to a PP unit. In this case, one of
the sources is under a shutdown and an alternative Source C is
used to meet the propylene demand.
Water
Oxygen
Methyl acetylene
Methanol
H
2
S
COS
CO
CO
2
C
4
dienes
Arsine
Propadiene
Acetylene
0 50 100 150
ppm for 20% catalyst activity reduction
200
FIG. 1. Catalyst activity reduction due to different poisons.
Water
Oxygen
Methyl acetylene
Methanol
H
2
S
COS
CO
CO
2
C
4
dienes
Arsine
Propadiene
Acetylene
0 20 40 60
Relative poison strength
80
FIG. 2. Relative poison strength.
Sulfur
removal
CO
removal
Dryer
Dryer
To PP plant
Propylene
Source A
Propylene
Source B
FIG. 3. Propylene source configuration.
C78 CATALYST 2013|HydrocarbonProcessing.com
CATALYST
FIG. 4 shows the effect on catalyst activity when Source A
(without CO guard beds) goes offline and then comes online
again. The daily average catalyst activity is plotted for an entire
month when the polymerization unit is running at the same
residence time and at the same H
2
con-
centration (same polymer grade) in a gas-
phase reactor.
FIG. 4 reveals that catalyst activity is ap-
proximately 25% lower when untreated
propylene feed Source A is online. This
translates into an additional cost of approxi-
mately $5 million/yr due to excessive cata-
lyst consumption.
FIG. 5 illustrates the effect that varying
CO levels in propylene feed Source A have
on catalyst activity for a period of nine days
on a real-time basis. The figure shows that the CO level is in-
creasing while catalyst activity is dropping. A loss of approxi-
mately 45% catalyst activity is seen when CO levels go up from
approximately 90 ppb to approximately 250 ppb.
FIG. 6 portrays a relationship in a commercial reactor be-
tween levels of CO in a propylene feed vs. catalyst activity when
other process parameters are kept constant. A simple extrapola-
tion yields a further activity rise by 10% to 13% if there is no CO
contamination in the propylene feed.
Solution. Since the source of the CO contamination was known
and the average CO level was confirmed by the online CO ana-
lyzer, it was easier to calculate lost revenue. Various options were
evaluated against the cost and feasibility of carrying out the change.
In FIG. 7, it was proposed to partially fill the existing dryer on
Source B with CO-removal catalysts. This proposal would save
on potential capital and construction costs associated with in-
stalling a new bed, associated piping and required plot space. All
operational aspects and regeneration were carefully evaluated
and documented accordingly.
The end result was a new mixed bed with a molecular sieve
and CO-removal catalysts. After commissioning, an immediate
increase was observed in catalyst activity.
10
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Date of month
Source A shutdown
Source A startup Source B+C Source A+B+C
Source A+B
17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
12
14
16
18
20
22
24
26
28
C
a
t
a
l
y
s
t

a
c
t
i
v
i
t
y
,

t
o
n
s

P
P
/
k
g

c
a
t
a
l
y
s
t
FIG. 4. Effect of untreated propylene source on catalyst activity.
FIG. 5. Effect of CO in propylene on catalyst activity.
CATALYST NEWS
NEW STEP-OUT CATALYST FOR ULSD AND
HYDROCRACKER PRETREAT
Haldor Topse has announced an improved catalyst prepa-
ration technology. In hydrocracking pretreatment and high-
pressure ULSD services, the catalyst exhibits 40% higher ac-
tivity than its predecessor. The higher activity can be used to:
Achieve longer cycles at the same feed rate
Process tougher feeds
Increase conversion to achieve lower product sulfur
Increase throughput.
The technology offers an improved production technique
for hydroprocessing catalysts. It combines previous technol-
ogy with a catalyst preparation step developed by Topses
research department. The combined effect from merging
the two technologies has led to a metal slab structure that is
characterized by an optimal interaction between active metal
structures and the catalyst carrier. As researchers from Topse
demonstrated in the 1980s, the activity of Type II sites is very
strongly influenced by this interaction. The technology affects
the way in which the metal slabs are bound to the carrier, re-
sulting in the activity of both the direct sites and the hydroge-
nation sites being increased significantly. These new catalysts
exhibit high stability with the added benefit of a step change in
hydrodesulfurization and hydrodenitrogenation activity.
NEW CATALYSTS CAN HELP AUTOMAKERS MEET
CARB LEV III EMISSION REGULATIONS
The California Office of Administrative Law recently ap-
proved the more stringent LEV III automotive emissions regu-
lations for new passenger vehicles proposed by the California
Air Resources Board (CARB). BASFs direct ozone reduction
catalyst systems can help automakers meet these increasingly
strict LEV III low-emission vehicle regulations.
When applied to heat exchange surfaces, such as car radia-
tors, the BASF system effectively turns them into smog eat-
ers. The catalyst reduces ground-level ozone in the air that
passes over coated surfaces by converting ozone molecules into
oxygen molecules instantly upon contact.
HYDROCARBON PROCESSING|CATALYST 2013 C79
CATALYST
As shown in FIG. 8, CO at the outlet of the bed decreased
from approximately 120 ppb to below 20 ppb. A quick analysis
based on the two month operation revealed a possible return on
investment in less than a year.
Keep it clean. To realize full activity from polymerization cata-
lysts, feed streams need to be as clean as possible from all con-
taminants and catalyst poisons. A very low level of even a single
catalyst poison can reduce catalyst activity drastically. In line with
the keep it clean philosophy, the feed treatment unit must be
carefully selected to treat all possible contaminants. The money
invested can give a quick return and the payback period can be
completed in as little as six to nine months.
HANIF POORKAR is a senior process engineer for Tasnee in Al-Jubail, Saudi
Arabia, where he has been employed for more than eight years. He has mainly
worked with different polypropylene process technologies throughout his 16 year
career. He holds a degree in petrochemical engineering from Dr. Babasaheb
Ambedkar Technological University in Lonere, India, and an MBA degree from
Karnataka University in India.
HAMAD AL-SHBRAIN is the polymer process engineering manager for Tasnee in
Al-Jubail, Saudi Arabia. He is a chemical engineering graduate with more than
16 years of experience.
SAAD AL-HARBI is an operations manager at Tasnee in Al-Jubail, Saudi Arabia.
He is a chemical engineering graduate and has worked for Tasnee for more
than 11 years.
ABDULLAH AL-SAEED is a chemical engineering graduate from King Saud
University in Saudi Arabia. He currently works as an operations manager for
Tasnee in Al-Jubail, Saudi Arabia.
FIG. 6. Relationship between CO and catalyst activity in a
commercial reactor.
Current
50-200 wt ppb CO
Molecular sieve
Molecular sieve
CO removal
catalyst
< 20 wt ppb CO
Proposed
FIG. 7. Present and proposed scheme for using existing bed with
two types of material.
Catalyst yield
Inlet CO ppm
Outlet CO ppm
Bed taken online
Improved catalyst mileage
0
3/21/2012 3/22/2012 3/22/2012 3/22/2012 3/22/2012 3/22/2012 3/23/2012
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
5
10
15
20
25
FIG. 8. Catalyst activity before and after mixed bed commissioning.
This is the first commercial product that destroys harmful,
ground-level ozone already in the air, said Nick Leclerc, prod-
uct manager for BASF Corp. The California Air Resources
Board recognizes it as an effective ozone-reduction strategy and
offers credits toward LEV III certification for car makers using
the technology.
Over three million vehicles are using this technology.
GRACE ACQUIRES NOBLESTAR CATALYSTS ASSETS
W. R. Grace has completed its acquisition of the assets of
Noblestar Catalysts, a Qingdao, China-based manufacturer of
fluid catalytic cracking catalysts, catalyst intermediates and re-
lated products used in the petroleum refining industry.
Qingdao is a leading economic center in China, said
Qingdao Bureau of Commerce Vice Director General Cong
Yan during a ribbon cutting ceremony. We welcome foreign
investment, especially from companies like Grace, which can
help develop our fast-growing petrochemical industry while
also acknowledging environmental and safety concerns.
The successful acquisition of Noblestars assets in Qingd-
ao is another milestone in Graces long relationship with Chi-
na, said Graces CEO Fred Festa. Our goal is for customers to
look to Grace for innovative technology and industry-leading
technical service, as well as a globally integrated manufactur-
ing network that aligns with the worlds demand.
Grace expects to make additional investments at the Qing-
dao site for environmental, safety and manufacturing upgrades.
We have been happy and proud to be a business partner
of Graces refining technologies business for years and we are
excited to continue a business relationship with Grace in the
future, said Chao Cui, CEO of Noblestar Catalysts.
Grace first established a presence in China when it founded
Grace China Ltd. in 1986 as one of the first foreign-owned
companies to do business in the country, through its can seal-
ants plant in Shanghai. Currently, Grace operates five manu-
facturing facilities, three sales offices and two technical service
centers in mainland China, including its Asia-Pacific regional
headquarters in Shanghai.
Stimulate the heart of
your hydroprocessing unit
Single source lSO 9001 lSO 14001 OHSAS 18001
www.axens.net
Impulse
TM
, the catalyst technology that combines
the stability you recognize with the activity you need
SPONSORED CONTENT HYDROCARBON PROCESSING|CATALYST 2013 C81
AXENS
THE PERFORMANCE IMPROVEMENT
SPECIALISTS
Axens is recognized as a worldwide technology benchmark for clean
fuels production, conversion solutions, aromatics and olefins production
and purification. The combination of the technology and services with
the catalysts and adsorbents manufacturing and supply business is an
efficient organization that handles market needs as a single source.
Currently, Axens offers a complete product range of hydrotreating
and hydroconversion catalysts from naphtha and gas oil to residue appli-
cations and continues to launch new catalysts to meet high conversion
and mild hydrocracking units objectives and to produce ultra-low sulfur
diesel (ULSD) while maximizing refinery profits.
HRK, HDK AND HYK SERIES HYDROCRACKING CATALYSTS
Axens commercial hydrocracking catalyst suite upgrades a wide
range of heavy feedstocks to produce the desired slate of products while
meeting ultimate quality targets. It relies on a combination of catalysts
derived from HRK, HDK Series (both for pretreating section) and HYK
Series (for hydrocracking section) depending upon operator conversion
targets. The combination of HRK, HDK and HYK Series enables to
squeeze more middle distillates from heavy ends while reaching high
conversion levels.
IMPULSE CATALYST TECHNOLOGY
With the improvement in fuel product specifications and increased
demand for middle distillates, hydrotreating catalyst technology has
become crucial to the refining industry. Axens has recently introduced
onto the market Impulse, a new catalyst technology leading to a
complete, high performance range of hydrotreating catalysts combining
stability and high level of activity. Impulse catalysts allows for even more
difficult feedstock to be processed without cycle penalty. They offer,
higher flexibility, maximum throughput with higher end boiling point and
longer cycles. Impulse achieves increased activity by maximizing the
amount of catalytically most active mixed Mo (Ni)/Co sites.
SULFUR RECOVERY CATALYST
Over the last 30 years, continuous Axens R&D efforts contributed to
a drastic change in the recovery of sulfur. Axens pioneered the use of
titanium dioxide catalysts to boost the efficiency of the Claus unit, and
our low temperature catalysts allow major energy and costs savings on
the Claus tail gas treatment units, and even a revolution in the way these
units are designed.
Axens brings essential support to its customers and offers a broad
range of innovative products in the field of sulfur recovery ranging from
Claus alumina (CR) or boosted alumina (CR-3S) for improved perfor-
mance, pure titanium dioxide catalysts (CRS 31, CRS 31 TL) and BTX
management catalyst (CSM 31) to Claus tail gas hydrogenation cata-
lysts. Our low temperature Claus tail gas treatment (TGT) CoMo catalysts
(TG 107 and TG 136) allow lowering the operation temperature while
maintaining TGT unit performances. As a result, energy consumption
and related CO
2
emissions are reduced and increase catalyst service
life is increased.
CONTACT INFORMATION
89, bd Franklin Roosevelt - BP 50802
92508 Rueil-Malmaison - France
information@axens.net
www.axens.net
Request your free chemical
value chain wall poster at
www.catalysts.basf.com/catalog
building blocks love
strong foundations
Todays petrochemical industry provides the building blocks
for a wide range of materials. As the global leader in catalysis,
BASF provides a strong foundation of product and process
innovations across the petrochemical value chain. The result is
a broad petrochemical catalyst and adsorbent portfolio backed
by dedicated customer and technical service and enabled
through the strength of BASF - The Chemical Company.
At BASF, we create chemistry for a sustainable future.
BASF
BASFSERVING THE HYDROCARBON
PROCESSING INDUSTRY FOR OVER 120 YEARS
From our invention of the contact process for sulfuric acid production in
1888 to the industrial catalytic process for ammonia in 1913 to commercializa-
tion of the three-way catalytic converter in 1974, BASF has played a vital role
in shaping the history of industrial catalysis. As the global leader in this field,
we continue to revolutionize the hydrocarbon processing industry and advance
chemical applications of all kinds, helping drive our customers success.
As a catalyst company, BASF can only be successful by working with
strong partners. We provide a comprehensive and cost-competitive portfolio
of leading catalytic technologies, which is constantly improved through inno-
vation. We use highly efficient platform technologies and high-throughput
catalyst-screening methods. This, in combination with dedicated R&D projects
in all regions, enables us to develop innovations quickly, in close collaboration
with our customers.
At BASF, we understand that the total value of our solutions must extend
beyond the product itself to include commercial and technical support, global
supply chain management and responsive customer service. Weve built a
commercial and technical team that has more than 300 years of combined
experience in the development and application of catalyst technologies across
the entire range of chemical processes. This expertise is further strengthened by
a global team of customer service providers, global centers of manufacturing
excellence, and the capability of the global BASF supply chain.
BASF is committed to partnering with its customers to understand the chal-
lenges faced by the global hydrocarbon processing community and we are
proud to continue our proven tradition of introducing sustainable solutions to
the market.
The result is a broad catalyst portfolio backed by dedicated customer and
technical service and enabled through the strength of BASFThe Chemical
Company. At BASF, we create chemistry for a sustainable future.
First defnition of
catalysis by Jns
Jakob Berzelius
Eugene Houdry
develops
fuid catalytic
cracking (FCC)
BASF develops the
contact process
for producing
sulphuric acid
1st refning
catalyst application
(Platinum reforming
catalyst for Sinclair
Oil Catforming
process)
Alwin Mittasch (BASF)
fnds the industrial
catalyst for production
of ammonia by
systematic tests of
several thousand
catalyst formulations
1st FCC Catalyst
produced
Fritz Haber, Carl
Bosch, and Alwin
Mittasch implement
the industrial scale
ammonia process
BASF received Frost
& Sullivan Award for
Technology Leadership in
recognition of Distributed
Matrix Structures (DMS) and
NaphthaMax
FCC catalyst
innovation
Franz Fischer
and Hans
Tropsch develop
the catalytic
hydrogenation
of carbon
monoxide to liquid
hydrocarbons
(gasoline)
BASF and Dow announced
the worlds largest
commercial-scale
propylene oxide (PO) plant
and the frst based on
the innovative hydrogen
peroxide to propylene
oxide (HPPO) technology
The three-way catalytic
converter for removing
pollutants from gasoline
engine exhaust is
commercialized by BASF
Rare Earth Alternative
(REAL) Solutions
introduced to cope
with high rare
earth oxide price
environment
Phinesse
introduced as
part of the REAL
program offering
lower rare earth
Adsorbents
Chemical Catalysts
Custom Catalysts
Environmental Catalysts
Polyolefn Catalysts
Precious Metal Services
Refnery Catalysts
Contact Us
Americas
catalysts-americas@basf.com
Asia Pacifc
catalysts-asia@basf.com
Europe, Middle East & Africa
catalysts-europe@basf.com
www.catalysts.basf.com
Understanding surface morphology gives
me an edge in my lab and in my garden.
Meet Josiane Ginestra:
Vegetable Grower. Catalyst Maker.
Customizing the surface of soil or a catalyst is equally critical when you want performance. No one
understands that better than Josiane Ginestra, CRITERIONs leading alumina scientist. Her 15+ years working
within Shells catalyst division has led to the development of a new generation of resid hydro-conversion
catalysts. Today youll nd Josiane overseeing the Canadian oil sands rening processes, continuing to help
develop custom solutions by reevaluating (and resurfacing) existing ones.
www.CRITERIONCatalysts.com
Leading minds. Advanced technologies.
CRITERION
THE NEXT BIG CHALLENGE
UNLOCKING VALUE FROM UNCONVENTIONALS
DAVID SHERWOOD, Senior Principal Scientist, Criterion Catalysts and Technologies
Unconventional heavy resources such as tar sands, shale oil and
heavy crude oil have yet to see extensive use in the marketplace because
of the processing challenges that they introduce. Meanwhile, the reserves
of conventional, easy-to-process crude oils continue to decline. One of
the next big challenges for the catalyst industry is to enable these ultra-
heavy oils to be processed with equivalent ease to conventional crudes.
The issue with these unconventional resources is not only that they
are heavy, viscous and often acidic, but that they also contain elevated
amounts of contaminants such as nickel, vanadium and nitrogen.
Although the industry is used to handling these elements, unconven-
tional resources typically have them at unprecedented high levels. They
also contain contaminants, such as arsenic, that have not historically
been an issue in refineries.
In addition, unconventional heavy crudes contain fewer valuable
distillates and their processing leaves more less-valuable residue, which
means that a greater conversion ability is required to transform the resi-
dues into the desired product slate.
This ties in with a second challenge faced by the catalyst industry:
how to increase the overall conversion of the residues of all crudes into
more valuable distillates. Worldwide, the demand for fuel oil is projected
to decrease, whereas the demand for clean transportation fuels is pro-
jected to increase. We need to get much more out of the bottom of the
barrel for both conventional and unconventional crudes.
Major focuses for Criterions residue upgrading teams are the devel-
opment of catalysts that can handle the extremely high levels of con-
taminants from the residues of unconventional crudes and increasing the
production of valuable distillates from all crudes.
The role of catalysis in residue upgrading cannot be overstated.
At Criterion, we have had a very strong focus on this for almost 30
years, secured several patents and become a world-leading supplier of
ebullated-bed catalysts. We will continue to target our research at devel-
oping catalysts that can facilitate the processing of heavier feeds and
help to raise residue conversion levels without sacrificing cycle length.
CONTACT INFORMATION
910 Louisiana Street, 29th Floor
Houston, TX 77002
Phone: +1 713 241 3000
david.sherwood@cri-criterion.com
www.criterioncatalysts.com
GRACE CATALYSTS TECHNOLOGIES/ADVANCED REFINING TECHNOLOGIES
LEADING WITH THE BROADEST PORTFOLIO
OF FCC AND HYDROPROCESSING CATALYSTS
Only Grace Catalysts Technologies (Grace) and Advanced Refining
Technologies (ART) offer refiners the broadest portfolio of high technol-
ogy, state-of-the-art FCC catalysts and additives and hydroprocessing
catalysts. Driven by our world-class research and development, together
Grace and ART have the manufacturing flexibility and technology to
customize products designed specifically to optimize FCC and hydro-
processing operations.
FCC: INVESTING IN THE GROWTH REGIONS
Grace is the global leader for FCC catalysts and additives, offering
solutions-oriented approaches backed by a broad, highly differentiated
portfolio and industry-leading technical service. Graces research leader-
ship and flexible manufacturing system support value-added technology
tailored to meet customers current and future needs.
Management of rare-earth inflation has been a major focus of the
RT business over the last several years. Due to our ongoing commitment
to Research and Development, Grace was able to launch eight no or
low rare-earth FCC catalyst and additives in early 2011 and saw rapid
market acceptance of the new technologies. The market has since expe-
rienced a similar rapid decline in rare-earth price, in response to new
supply of the light rare-earth elements, and weak demand as a result of
substitution efforts in both FCC and other industries. FCC customers are
beginning to shift back to higher rare earth in their catalyst formulations;
however many customers choose to remain on the low rare-earth formula-
tions due to the realized yield benefits.
In May 2012, Grace announced its intent to form a joint venture with
Al Dahra Agricultural Company to build and operate a fluid catalytic
cracking catalysts and additives plant in the Middle East. The plant in
Abu Dhabi would be the first FCC catalysts and additives plant in the
region, and is an important step for Grace to reinforce the reliable and
timely distribution of FCC catalysts and additives to refineries in the
region. There are expected to be 16 FCC units built in these regions in
the next five years, which would increase the catalyst opportunity in the
region by approximately $150 million.
In May 2012 Grace announced the acquisition of Noblestar Cata-
lysts Co., Ltd, a manufacturer of fluid catalytic cracking (FCC) catalysts,
catalyst intermediates, and related products used in the petroleum refin-
ing industry located in Qingdao, China. This acquisition provides Grace
with immediate, local manufacturing capacity to better serve our refining
customers within China and North Asia.
HYDROPROCESSING: FOCUS ON R&D LEADS TO
FOUR NEW CATALYSTS FOR 2013
Advanced Refining Technologies (ART), the joint venture between
Chevron Products Company and Grace, was created to develop state
of the art hydroprocessing catalysts. ART combines Graces material
science, manufacturing, marketing and sales strength with Chevrons
extensive experience operating its own refineries and leadership in
technology, design and process licensing.
ART continues to grow and plan for the future, having recently intro-
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enhanced ULSD run length and 425DX for enhanced ULSD performance
at low pressure. For fixed bed resid hydrotreating units, ICR 173 is a
new deep MCR and S conversion catalyst, and HCRC (High Catalytic
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conversion for ebullating bed resid hydrocracking units.
In addition, ART is expanding and upgrading its plants to produce
these new catalysts and future ones that are currently under development.
These products are being designed to help refiners meet the challenges
of the expected growth in demand for diesel and other low-sulfur fuels,
while continuing to further upgrade the bottom of the barrel.
In addition to its manufacturing facilities in the United States and
Japan, ART serves the Middle East/Arabian Gulf region through a key
toll manufacturing partnership with Kuwait Catalyst Company, in which
it also owns an equity stake.
CONTACT INFORMATION
7500 Grace Drive
Columbia, MD USA 21044
Fax: +1 410.531.4540
www.grace.com; www.artcatalysts.com
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Refining Developments
L. MCDERMOTT, Applied Instrument
Technologies, Inc., Upland, California; and
A. MALIK, Phillips 66, Roxana, Illinois
Improve benzene control
The US Environmental Protection Agency (EPA) issued
the Mobile Source Toxics (MSAT) Rule on February 26, 2007
(40 CFR Parts 59, 80, 85 and 86). This rule required refiners to
reduce the average benzene concentration in the gasoline pool
to 0.62 vol% or less by January 1, 2011. Refiners producing
higher levels could reduce their concentration by purchasing
credits, but they are capped at a maximum actual average con-
centration of 1.3 vol%.
The MSAT ruling has led many refineries to upgrade pro-
cessing to meet the new benzene limits. Because the majority
of benzene in blended gasoline (by some estimates 70%85%)
originates from reformate, reducing the benzene levels in the
reformate offers the most direct means to meet specifications
for finished gasoline.
1
The refinery. The Phillips 66 Wood River refinery in Roxa-
na, Illinois, is a 365,000-bpd facility. In 2008, the refinery (a
ConocoPhillips refinery at the time) evaluated options to
meet the MSAT ruling. The plant decided to install a refor-
mate splitter column to treat reformate produced by the re-
finerys catalytic reformer. This technique is a post-fraction-
ation process. Benzene is concentrated in the heart cut of the
splitter containing 20%30% of benzene. The benzene can
be removed from the blending pool either by saturation or by
additional concentration via extraction to produce a sellable
high-purity benzene product.
Selection criterion. To optimize performance of the benzene-
reduction process and to ensure that the reformate complied
with new blending pool specifications, the Wood River project
team evaluated several analyzer technologies for real-time anal-
ysis. The refiner selected two technologies: process gas chroma-
tography (PGC) and Fourier transform infrared (FTIR) spec-
troscopy. The technology selection phase focused on:
Ability to make the required analytical measurements.
Both the PGC and FTIR systems were capable of measuring
benzene and toluene at the required levels.
Site familiarity with technology and ability to support
systems. The Wood River refinery has numerous PGC systems
installed throughout the refinery, and it also had installed spec-
troscopic near-infrared (NIR) analyzers on the gasoline blend-
ers since 2001. The site recently added online NIR analysis of
the diesel blending stream.
Cycle time. Spectroscopic analyzers like the installed
FTIR system have typical cycle times of 12 minutes per stream.
To meet the required cycle time for the broad dynamic range of
required measurements, four PGC systems would be required.
Cost. By using one FTIR system with two measurement
flow cells (one for high-concentration analysis streams and one
cell for measurement of low-concentration streams), the FTIR
system cost was lower than that to install four PGCs. Addition-
al cost savings for the FTIR system were calculated based on
lower maintenance and utility requirements.
To measure, control and optimize the reformate splitter col-
umn, Phillips 66 installed an online multistream FTIR analyzer
to monitor six streams of the unit. FIG. 1 is a diagram of the split-
ter column, highlighting the analyzed streams. The light-refor-
mate feed, heavy-reformate feed, side-draw feed to the benzene
extraction unit, lower side-draw, tower bottoms and splitter top
streams are analyzed by a two-cell FTIR system installed in a
shelter near the unit.
The FTIR system was specified to monitor the benzene,
toluene and butane concentrations. The analysis slate was
modified to add the analysis of distillation points, aromatics
Light feed
Toluene concentrate
RDC-1 feed
Heavy reformate product
Splitter tops
Heavy feed
FIG. 1. Benzene-extraction unit indicating analyzed streams.
and research octane number (RON) for the toluene concen-
trate stream. Measuring butanes was not developed because of
the difficulty in reliable sample handling and also the determi-
nation that there was limited value in using the butanes data in
the unit control scheme.
Analyzer system. A dual-stream, extended-range mid-infra-
red process FTIR analyzer was installed on the splitter column.
The six incoming streams were plumbed to the analyzer shel-
ter. Sample conditioning systems were installed on the exterior
wall of the shelter to remove particulate materials and water
from the streams. The conditioning system also provided tem-
perature control of the sample. A stream switching manifold is
used to select the streams to be analyzed. The analyzer system
is linked to the distributed control system (DCS) through a
Modbus TCP connection.
The DCS system is used to activate streams, allowing the
system to only measure required streams. The analyzer auto-
matically cycles through selected active streams. During rou-
tine operation, the two cells are alternatively analyzed. While
one analysis cell is being measured, the second cell is flushed
out with the next stream to be analyzed. The system was
configured with a pneumatically actuated optical switch con-
trolled by the main analyzer control program, which automates
system data collection and analysis, cell selection, validation,
automatic background collection and data reporting. An au-
tomated sample-cell wash and validation system was installed
to confirm proper system performance, and it allows for auto-
matic sample-cell washing in the event of window fouling. FIG.
2 is a block diagram of the analyzer system.
Calibration. A laboratory FTIR system was installed in the
Wood River laboratory shortly after the decision was made
to install the online analyzer. During the time that the process
analyzer was being built and installed, all routine samples for
the six streams were collected and taken to the lab for analy-
sis by conventional analyzers to determine the property values
of interest. The samples were also scanned on the lab FTIR
system. When the operators ran the samples on both the lab
and conventional analyzer systems, the laboratory information
management system (LIMS) number was entered, allowing
for easy integration of lab data with the FTIR scans. The FTIR
system logged collected data and sample information into a file
that was used in PC software to create a calibration database.
The laboratory system uses the same optics, interferometer
and sample analysis cell as used in the online system. The ex-
tremely high accuracy of FTIR-based systems allows for seam-
less transfer of data and models between systems; it ensures that
the models developed based on samples scanned on the lab sys-
tem can be used directly online. The FTIR spectra were collected
from 6,000 cm
1
to 1,000 cm
1
(1,667 nm10,000 nm) using a
0.5-mm pathlength transmission cell. Representative calibration
spectra for the six streams are shown in FIG. 3. The spectra for
the different streams are colored as indicated in the legend. The
large differences in the spectra for the different streams are due
to the large compositional differences for the six streams. Initial-
ly, it was thought that it would be possible to combine data from
several streams to minimize the modeling effort. A principal
components analysis (PCA) was performed on the combined
data set to investigate any relationships between the streams. FIG.
4 is a score plot of the first two factors. The six sample streams
Plant DCS system
Lab FTIR
analyzer
S
a
m
p
l
e

p
r
e
c
o
n
d
i
t
i
o
n
i
n
g
e
n
c
l
o
s
u
r
e
S
a
m
p
l
e

p
r
e
c
o
n
d
i
t
i
o
n
i
n
g
e
n
c
l
o
s
u
r
e
FTIR analyzer optical
and electronic enclosure
FTIR dual-cell
enclosure
Heavy reformate feed
Toluene concentrate
Heavy reformate
Light reformate feed
RDC feed
Splitter tops
Laboratory LIMS
Analyzer shelter
Class 1, Group D, Division 2, T2c
Val Wash
Wash/validation skid
Modbus
FIG. 2. FTIR installation diagram.
FIG. 3. FTIR spectra for calibration samples.
Heavy feed
RDC-1
Toluene concentrate
Heavy reformate
Splitter tops
Light feed
-5 0 -5
-2
0
2
Factor 1 (80.5%)
F
a
c
t
o
r

2

(
1
0
.
5
%
)
FIG. 4. Score plot for calibration samples.
can be seen to be different enough in score spacing to discourage
efforts to combine sample streams into any grouped or common
models. Calibration models were developed for each stream,
and the results were significantly better than the results obtained
when data from similar streams was combined.
Calibration models were developed using chemometric
modeling software.
a
This software uses the principal compo-
nents regression (PCR) algorithm and incorporates advanced
data-filtering techniques to reduce or eliminate interferences
such as those caused by ambient carbon dioxide and mois-
ture, baseline effects and possible pathlength variations. The
software was evaluated to investigate additional data process-
ing and calibration capabilities. The spectral regions that are
saturated or which contain little or no relevant information for
TABLE 1. Calibration table summary
Concentration range
Stream Property APC Use Units Min Max Samples Factors SEE SECV R
2
BRU heavy feed Benzene Monitor vol % 2.65 7.28 60 3 0.192 0.208 0.978
BRU heavy feed Toluene Monitor vol % 12.2 21.1 58 4 0.63 0.7 0.914
BRU rdc-1 feed Benzene Monitor vol % 25 40.5 85 4 0.77 0.81 0.944
BRU rdc-1 feed Toluene Control vol % 0.02 2.12 76 4 0.121 0.125 0.946
BRU toluene concentrate Benzene Monitor vol % 0.02 1.85 93 4 0.07 0.083 0.92
BRU toluene concentrate Toluene Monitor vol % 35 67.45 102 4 1.49 1.54 0.918
BRU toluene concentrate RON # Control ON 99.65 113.5 100 5 0.736 0.787 0.916
BRU toluene concentrate Distillation 50% Control F 235.7 257.5 98 3 1.05 1.1 0.941
BRU heavy reformate product Toluene Control vol % 3 37.65 108 3 1.35 1.39 0.972
BRU splitter tops Benzene Control vol % 0.23 2.04 56 4 0.1 0.107 0.97
BRU light feed Benzene Monitor vol % 10.95 18.5 90 3 0.5 0.52 0.926
BRU light feed Toluene Monitor vol % 20.76 29.76 87 4 0.736 0.776 0.82
0.0 0.5 1.0 1.5 2.0 2.5
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
Toluene measured by lab, %
T
o
l
u
e
n
e

p
r
e
d
i
c
t
e
d
,

%
RDC feed
FIG. 5. Correlation between model-estimated and lab-determined
toluene for RDC feed.
98 100 102 104 106 108 110 112 114
98
100
102
104
106
108
110
112
114
RON measured by lab, %
R
O
N

p
r
e
d
i
c
t
e
d
Toluene concentrate
RON for the toluene concentrate stream.
235
Distillation point measured by lab, %
Toluene concentrate
D
i
s
t
i
l
l
a
t
i
o
n

p
o
i
n
t

p
r
e
d
i
c
t
e
d
,

5
0
%
235
240
245
250
255
260
235 240 245 250 255 260
50% distillation point for toluene concentrate.
0
0
Toluene measured by lab, %
T
o
l
u
e
n
e

p
r
e
d
i
c
t
e
d
,

%
5 10 15 20 25 30 35 40
5
10
15
20
25
30
35
40
Heavy reformate
toluene for heavy reformate.
the property of interest, were excluded from the calibration. All
calibrations were developed using random subset cross valida-
tion. Models were developed generally following the recom-
mendations of ASTM E-1655, Standard Practices for Infrared
Multivariate Quantitative Analysis. A minimum number of out-
lier samples were identified and removed from the calibration
sets. Several of the removed outliers were based on incorrect
sampling; others were identified as misidentified samples.
TABLE 1 summarizes the results of modeling. For all mea-
surements examined, a strong correlation (R
2
) was attained
between the spectral response and the primary values, and the
standard error of cross validation (SECV) essentially matched
the standard error of estimate (SEE). All models used a sig-
nificant number of calibration samples, ranging from 56 to
108 samples. The number of factors used for all models varied
from 3 to 5. The optimum number of factors was selected by
evaluating the predictive residual error sum of squares plots,
loadings and regression vectors calculated to avoid over-fit-
ting of the data.
Streams listed as control in TABLE 1 are used for advanced
process control (APC) of the splitter column. FIGS. 59 show
the strong correlation (fit) obtained for several of the key con-
trol properties used.
Control. The FTIR analyzer provides product stream analysis
that is used in an APC application to maximize recovery, and
to reduce energy at the benzene-removal unit (BRU) column.
The controlled variables of this application are:
Percent benzene in the overhead liquid product
Percent toluene in the feed to the extraction unit
RON of the toluene concentrate stream
50 % Distillation point of the toluene concentrate stream
5% Distillation point of the toluene concentrate stream.
The other calibrated properties are used for monitoring the
system and are not actively used in the APC logic. However,
they are available to operators and control engineers through
the DCS system. All data are archived in the plant historian.
A single FTIR system has been installed to analyze six
streams on a reformate splitter column. Calibration models
were developed and installed to monitor the concentration of
benzene and toluene, as well as additional properties, includ-
ing the RON and several distillation points. The accuracies at-
tained using the FTIR system are comparable to those attained
using the conventional analytical techniques. The system was
installed to meet the MSAT deadline, and it has enabled the
Wood River refinery to meet the regulated MSAT specifica-
tion for blended gasoline and to optimize operation of the
splitter column.
LITERATURE CITED
1
Palmer, R. E., Options for reducing benzene in the refinery gasoline pool, 2008
NPRA Annual Meeting, San Diego.
2
McDermott, L., Cetane benefits, Hydrocarbon Engineering, July 2003, Vol. 8 No.
7, pp. 6973.
3
Cutting through the haze: How will refiners meet EPAs new benzene standards?,
Benchmark Newsletter, 2007.
4
Uvland, K. A., Oil and Gas Process International, 1997
5
Vickers, G. H., On-line determination of naphtha properties to control a refinery
process using near infrared spectroscopy, IFPAC Conference, 2001.
NOTES
a
Calibration models were developed using chemometric modeling software avail-
able from Applied Instrument Technologies.
DR. ATIQUE MALIK holds a BS degree and PhD in chemical engineering from
the University of Leeds. He has worked in the area of model predictive control
for various companies. Dr. Malik has reviewed publications for the Journal of
Process Control and has been associate editor for Control Engineering Practice.
He is the team Lead for APC at the Wood River Phillips 66 refinery.
LARRY MCDERMOTT holds a BA degree in chemistry, an MS degree in marketing
and technological innovation and an MS degree in management engineering.
He has worked in the field of process analyzers based on spectroscopic systems
for over 20 years. He is the technical applications manager for Applied Instrument
Technologies, focusing on chemometric modeling of refinery process streams.
Benzene measured by lab, %
B
e
n
z
e
n
e

p
r
e
d
i
c
t
e
d
,

5
0
%
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
0.0
0.5
1.0
1.5
2.0
2.5
Splitter tops
benzene for splitter tops.
Centrifugal Pump Pac is a complete program
designed for centrifugal pump engineers.
This program provides commercially
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CPPAC
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Clean Fuels
C. POUWELS, Albemarle Catalysts, Amsterdam,
The Netherlands, K. BRUNO, Albemarle Corp.,
Houston, Texas
FCC catalyst design evolves to maximize propylene
The growing demand for propylene has intensified interest
in maximizing propylene from refinery fluid catalytic cracking
units (FCCUs). Refiners in Asia and the Middle East are setting
the pace, with numerous new FCC units planned or already on-
stream to take advantage of this opportunity. Each of these new
units includes the most modern technology to achieve record
high propylene and conversion.
On one hand, new records are set in the heaviness of feeds
posing challenges to maintain activity; conversely, some FC-
CUs are specifically designed for low sulfur (hydrotreated)
gasoil (GO) feeds that impose a real challenge to meet the heat
balance requirement of the FCCU. Achieving record high pro-
pylene yield and conversion from a wide range of feed quality
offers considerable challenges to the catalyst design, as well.
High accessibility (diffusion), advanced zeolite and low rare
earth (RE) technologies are critical components of modern
catalyst designs required to meet the desired objectives. Also,
the feed composition impact and process variables on the yields
and heat balance are significant and thus requires a good under-
standing of the chemistry to design the right FCC catalyst for
individual FCCUs.
Naphtha cracking played a dominant role in manufacturing
propylene for a long time, but the primary product is ethylene.
The growth rate of propylene demand is outpacing that of eth-
ylene. More recently, the FCC process is often a better solution
for refiners to invest in. The FCC process has become a major
refinery process to generate propylene. With many new units an-
nounced and several units already in the process of engineering
and construction, the importance of the FCC process to meet
the growing propylene demand will increase. These new FCC
units often operate at higher severity and up to the edge of what
is possible today. The highest reactor temperatures and very high
levels of shape selective ZSM-5 additives are almost never suffi-
cient to meet new propylene targets, which seemingly hover at a
plateau due to over-cracking, activity dilution and the absence of
key catalyst design features. Many refiners are facing this plateau
and have difficulty lifting the yield of propylene. A good under-
standing of the cracking mechanisms involved is required, as is
a focus on the quintessence of FCC catalyst design to maximize
propylene yield and the mechanisms of propylene generation.
Understanding the mechanisms. In the refining industry,
several cracking processes are applied to cleave carbon-carbon
bonds: hydrocracking, thermal cracking and, most importantly,
catalytic cracking. Hydrocracking will not be discussed further
as it is of nearly no importance for the production of propylene.
Cracking is either an acid catalyzed or a thermal, not a catalytic
process. Though FCC is predominantly a catalytic process,
some thermal reactions also take place.
Thermal cracking proceeds through a free radical process
and involves three steps: initiation, propagation and termina-
tion. At high temperatures, radicals are formed in the initiation
step. These radicals react further whereby ethylene is formed
and new radicals, leading predominantly to ethylene, followed
by methane and propane.
Catalytic cracking, however, makes use of acid sites in the
FCC catalyst and involves carbocations intermediates. More-
over, in FCC, a higher degree of branching is found, giving evi-
dence to isomerization reactions. FIG. 1 compares the products
of thermal and catalytic cracking of n-hexadecane at 500 C.
1
In
thermal cracking very little branched products are found.
Looking back in FCC history, some remarkable changes
occurred when going from amorphous cracking catalysts to
zeolite-based cracking. This step change in the FCC catalyst
technology led to a drastic increase in gasoline yield. Those are
all improvements that were highly desired from the FCC pro-
cess. But at the same time, the gasoline research octane number
(RON) dropped dramatically, which was associated with the
lower olefin content of the gasoline.
These yield and quality shifts were attributed to hydrogen
transfer (HT) reactions, by which initially formed olefins are
converted to more stable paraffins. And while gasoline olefins
0
20
40
60
80
100
120
140
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14
C-number
M
o
l
e
s

p
r
o
d
u
c
t
/
1
0
0

m
o
l
e
s

c
r
a
c
k
e
d
Thermal cracking quartz chips
Catalytic cracking amorphous SiO
2
/Al
2
O
3
FIG. 1. Comparison of products observed in thermal and catalytic
cracking of n-hexadecane at 500C.
Clean Fuels
were reduced, light olefins also decreased with the change to
zeolite-based cracking (TABLE 1).
HT is a bimolecular reaction, whereby hydrogen is, for in-
stance, transferred from naphthenes to olefins, producing par-
affins and aromatics. Brnsted acid sites of the Y-zeolite play
a crucial role in these reactions. Catalyst manufacturers have
several tools to optimize the characteristics and functionality
of the Y-zeolite, such as unit cell size (UCS), silica-to-alumina
ratio (SAR) and content of RE and sodium.
For the generation of propylene, other shape selective zeolites
exist and are commonly applied. For example, the invention of
ZSM-5 created another step change in FCC catalyst technology.
Since then, other proprietary advanced zeolite technologies have
been developed for maximum propylene applications.
12
Howev-
er, because it is well-documented public knowledge that ZSM-5
additives are effective to create light olefins, including propylene,
the fundamental chemistry discussed here will use ZSM-5 to
help illustrate the mechanisms of propylene production.
Zeolite, such as ZSM-5 with a pore entrance smaller than of
Y-zeolite, drives different catalytic reactions. The smaller pores
restrict the access of branched and cyclic hydrocarbons into its
interior and allow straight-chain and mono-methyl paraffins
and olefins to enter, hereby generating predominantly propyl-
ene and also butylenes and ethylene. The reactants are particu-
larly in the C
6
and C
7
range, but other gasoline molecules with
a carbon atom number between 5 and 10 can also be converted
by ZSM-5 to some extent. FIG. 2 shows clear evidence of the in-
creased production of C
3
, C
2
and C
4
, and the strong reduction
in C
6
and C
7
components.
FCC gasoline can be typically classified into five types of hy-
drocarbons: paraffins (P), isoparaffins (iP), olefins (O), naph-
thenes (N) and aromatics (A). Taking a closer look at the dif-
ferent types shows that isoparaffins and olefins with six or seven
carbon atoms are mostly cracked by ZSM-5 (FIG. 3). When an
olefin is cracked by ZSM-5, two smaller olefins are produced.
The generation of C
6
and C
7
olefins in the primary cracking steps
of FCC is therefore a valuable mechanism that needs managing.
The numbers on the bars in FIG. 3 show a reduction in the
specific hydrocarbon type. The decrease in light isoparaffins is
the largest, but this is speculated to be due to reduced forma-
tion of light isoparaffins in the presence of ZSM-5 and other
reactions, including cracking to light olefins. The light olefins,
however, contribute the most to propylene make, as olefins are
more reactive and they crack to form two smaller olefin mol-
ecules. In general, gasoline-range olefins are the primary reac-
tants for propylene.
The molecules that can be readily cracked by ZSM-5 are in
the gasoline boiling range and are often referred to as light-ole-
fin precursors. Though isoparaffins are good light-olefin pre-
cursors, the small pores of ZSM-5 restrict access to only those
paraffins with a methyl branch. Longer branches or multiple
branches are consequently undesirable. As Y-zeolite catalyses
isomerization reactions, these reactions should be carefully
controlled. The right-hand end of the x-axis in FIG. 3 shows
benzene and methylbenzene, which are two of the few gasoline
components to increase slightly with the use of ZSM-5.
FCC manufacturers have a variety of tools available for de-
signing the optimal catalyst for maximum propylene applica-
tions, as these different catalyst components affect cracking,
HT and isomerization.
Y-zeolite is the component most talked about. Its acidity is
high and contributes to a high level of cracking. Though Y-zeo-
lites can be varied in terms of UCS, RE content and SAR, their
HT activity is relatively high, and they also possess some isom-
erization activity. Lower RE content is thus strongly preferred
for lowest HT.
ZSM-5 zeolite is also very high in acidity and thus has high
cracking activity, though the cracking rate is highly determined
by the size and shape of the reactants. Its high SAR is also re-
sponsible for isomerization. Conversely, ZSM-5 has oligomer-
ization activity, whereby propylene can be consumed.
Finally, matrices play another crucial role in FCC catalysis.
Matrices are predominantly known as the components respon-
sible for pre-cracking large molecules before they enter the zeo-
lites. A wide range of matrices that vary in functionality, such as
bottoms conversion capability and metal capturing power, can
be applied. With their differences in functionality, the acidity is
different and can be rated as low to moderate compared to Y-
zeolite. Their cracking activity varies from low to high, while the
HT is typically lower than that of Y-zeolite, as is the isomeriza-
tion rate. FIG. 4 compares two different matrices, with different
0
2
4
6
8
10
12
14
16
18
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12
C-number
Y
i
e
l
d
,

w
t
%
FCC catalyst
FCC catalyst + ZSM-5
FIG. 2. The effect of ZSM-5 on products distributed by carbon number.
-2.8 -2.1 -2.0 -1.7 -1.5 0.3 0.5
0
1
2
3
4
5
iP6 O6 iP5 iP7 O7 A7 A6
C-numbers and component type
Y
i
e
l
d
,

w
t
%

o
n

f
e
e
d
FCC catalyst
FCC catalyst + ZSM-5
FIG. 3. Gasoline components that are most and least affected by ZSM-5.
TABLE 1. The change from amorphous cracking catalyst
to zeolite-based cracking leads to lower olens
Conversion Gasoline, vol% Propylene, vol%
Silica-alumina gel 75.5 47.5 8.5
REHY 85.5 61.0 5.9
Clean Fuels
HT power. The one lowest in HT (as shown on the second Y-
axis) leads to the highest C
3
=
.
Next to HT, several other secondary reactions take place,
such as cyclization and aromatization reactions. Moreover,
propylene molecules can undergo oligomerization reactions,
which means it is possible that propylene can be consumed and
its yield decreases.
2
Longer residence times are detrimental for
maximum propylene yields.
In summary, several factors must be controlled for maxi-
mum propylene yield:
1. Maximize generation of gasoline precursors, which are
predominantly C
6
and C
7
olefins and iso-paraffins
2. Minimize HT, which consumes valuable olefins
3. Control isomerization reactions to form methyl branches
4. Minimize other unwanted secondary reactions, such as
cyclization, aromatization and oligomerization.
Optimizing unit conditions. The FCC process is very ver-
satile and has the flexibility to be operated in different modes
which fit specific yield slates and meet market demands. To
achieve maximum propylene, the FCC unit is typically oper-
ated in a high-severity mode, whereby a high conversion is
achieved through high reactor temperature and high cat-to-oil
ratios. These parameters can be optimized by the operators with
relative ease. Other conditions that positively influence the pro-
pylene yield are low hydrocarbon partial pressure and/or high
steam partial pressure, use of naphtha recycle and the choice of a
hydrogen-rich feed. The latter options, however, are not always
easy to control. While process conditions can elevate the propyl-
ene yield by a few percent, the choice of the catalyst or catalyst
system can have a much larger impact on propylene, on the order
of 6 wt%8 wt% additional propylene on feed.
A high-severity operation is most favorable for propylene
production. When unit limitations permit, the highest reactor
temperature is commonly applied. Increasing reactor tempera-
ture, however, also enhances thermal cracking reactions, with
consequently more dry-gas production. A ratio that is commonly
looked at in FCC is C
4
/(C
3
+ C
4
). A ratio of 0.68 denotes a high
degree of catalytic cracking, whereas values near 0.50 indicate a
high contribution of thermal cracking.
3
(These values are appli-
cable to FCC catalysts not designed for maximum propylene.)
The effect of temperature on additional propylene make is
dependent on the starting condition. In maximum propylene
applications, reactor temperatures are already quite high and
the amount of ZSM-5 is substantial. Under those conditions,
the effect of an increased reactor temperature of 10C modestly
enhances propylene yield by about 0.8 wt%0.9 wt%, as shown
in TABLE 3.
It is generally accepted that cracking processes have higher
effective activation energy than bimolecular HT reactions, so
raising the reactor temperature increases the tendency for gaso-
line olefins to crack to light olefins rather than to undergo HT.
4
The impact of temperature on propylene make is evident in
a thermal cracking process. Also, high severity FCC-type cata-
lytic processes operate under much higher temperatures than
FCC in order to maximize propylene.
5, 6, 7
The effect of feedstock is important. Though a refiner may
not have a wide choice of options, any considerations are valu-
able. It is generally accepted that cleaner feeds with higher hy-
drogen content are easier to crack and increase propylene yield
through higher conversion. Unwanted are feeds that are high
in aromatics, since these components cannot be converted to
gasoline precursors and thus not lead to propylene. A poten-
tially attractive option to consider, though, is the use of recycle
streams of specific components which are valuable as reactants
for propylene production, such as light naphtha recycle or the
addition of products of C
4
/C
5
oligomerization. These can ei-
ther be added in the main riser or, even better, in a second riser
when present.
An interesting case for demonstration purposes was pre-
sented in 2007, in which Fisher Tropsch (FT) wax was cracked
in a pilot plant.
9
Blends in different ratios of equilibrium cata-
lyst and ZSM-5 additive olefins and octane maximization are
applied. High conversion rates are obtained due to the high
crackability of FT wax. While in common FCC operation the
FCC catalyst contributes to the highest conversion. With the
use of pure ZSM-5 additive, conversion levels above 90 wt% are
achieved with a propylene yield of 18 wt%, as shown in TABLE 5.
Catalyst design considerations. With the understanding
of the chemistry and influence of operating conditions, what
catalyst design should be applied for optimum propylene? In
FCC, there is no generic design that fits all, since all FCC units
9
11
13
15
17
40 50 60 70 80 90
Conversion, wt%
C
3
=

y
i
e
l
d
,

w
t
%
0.00
0.10
0.20
0.30
0.40
H
T
I
C
3
=
: Matrix 2
C
3
=
: Matrix 1
HTI: Matrix 2
HTI: Matrix 1
FIG. 4. Comparing the effect of different matrices on HT and
propylene yield.
TABLE 2. Comparing FCC key components
Acidity Cracking HT Isomerization
ZSM5-Zeolite Very high High* High
Y - Zeolite High High High Moderate
Matrices Low-
moderate
Low-High Low to
moderate
Low
*Size and shape of molecules determines cracking rates
TABLE 3. The efect of reactor temperature on propylene yield
Unit 1 Unit 2
Reactor temp., C 522 543 519 530
C
3
=
, wt% Base +1.6 Base +1.0
C
4
/(C
3
+C
4
), - 0.58 0.56 0.59 0.57
*FCC catalyst with high ZSM-5 content
Clean Fuels
and operations are unique. Important is a good understanding
of the specific unit, its constraints and the bigger picture of the
type of operation, for instance, with respect to cleanliness or
contamination of feed.
ZSM-5 additives are a very effective solution for increasing
propylene yield in the FCC unit. This approach gives the refiner
a great deal of flexibility, as additive usage can be adjusted ac-
cording to changes in propylene demand and to optimize opera-
tion within unit constraints such as wet-gas compressor loading.
As explained before, ZSM-5 generates propylene by se-
lectively cracking olefins in the gasoline boiling range. As the
amount of ZSM-5 additive in the catalyst inventory increases,
the incremental yield of propylene produced per percent of
additive decreases. Propylene yield reaches a plateau once the
ZSM-5 crystal concentration in the catalyst inventory reaches
around 10%. The diminishing effectiveness of ZSM-5 at higher
concentrations occurs largely because olefins in the gasoline be-
come depleted.
It is the base FCC catalyst design and technology, not ZSM-
5 concentration, that define the maximum propylene yield that
can be achieved in the FCC unit. FIG. 5 shows the amount of
propylene produced by a variety of ZSM-5 additives when used
with four different host FCC catalysts. The yield response of
the ZSM-5 changes according to the properties of the host cata-
lyst, and at high concentrations of ZSM-5, the propylene yield
reaches a plateau level that is determined solely by technology
inherent in the base catalyst.
The pore size of zeolite is too small for access by feed mol-
ecules, and so FCC catalysts contain some alumina matrix
components to pre-crack the feed into smaller components.
The product of this primary cracking by the matrix is very ole-
finic, and generates the gasoline olefin precursors that are then
cracked into light olefins.
We can estimate the relative activity of FCC catalyst for gen-
erating secondary reactions, using the hydrogen transfer index
(HTI) for catalysts tested under constant conditions with the
same feed. The HTI can be defined in several ways. One of
them is the ratio of isobutane over total C
4
s.
Catalysts with a lower HTI generate fewer secondary reac-
tions, and more gasoline olefins are preserved for cracking into
light olefins. The four base catalysts tested in FIG. 5 demon-
strate the effect of HTI on propylene generation, with propyl-
ene yield increasing as the HTI of the base catalyst is reduced.
Further testing under constant conditions demonstrates that
suppressing HT is the key to maximizing propylene. In FIG. 6,
multiple catalysts were mixed with varying amounts of ZSM-5
additive. The relative propylene shows a strong correlation with
the HTI of the base catalyst.
As suggested by the correlation obtained in FIG. 6, suppress-
ing HT reactions is the key to maximizing propylene yield, by
maximizing the availability of olefin precursors for cracking.
There are several ways that catalyst properties can be modi-
fied to suppress HT reactions. It is acid sites density and the
close proximity of these acid sites in the zeolite that promote
HT. One approach is to reduce the number of these acid sites
by lowering the zeolite UCS. A lower zeolite UCS is typically
achieved by reducing the RE content. A consequence of reduc-
ing catalyst zeolite content or UCS is a reduction in catalyst ac-
tivity for conventional catalyst technologies.
Low RE technology is critical to enable both maximum pro-
pylene yield and overall performance at a lower UCS, or equiva-
lently lower RE.
10
Specialized low RE systems deliver minimum
HT without the conventional loss in activity and therefore prof-
itability
11
Key features for success include a high zeolite SAR for
maximum stability; advanced zeolite technology for propylene;
strong, selective matrices for cracking with minimal HT; and a
TABLE 4. Example showing efect of hydrocarbon partial
pressure on propylene yield
RxT, C 553 551
RxP, barg 2.1 2.8
Steam, mol% on feed 71% 60%
C
3
=
, wt% on feed 11.6 9.9
TABLE 5. Cracking FT-wax in FCC pilot plant leads to high
propylene yields
Feed properties Operations
Type FT-Wax Unit Pilot plant
API, 43.1 RxT, C 538
SG 0.81 CTO 4
S, ppmw 2.5 Catalyst ZSM-5 additive olens
and octane maximization
Sim Dist, 5%, C 368 Conv, wt% 92
Sim Dist, 95%, C 474 C3=, wt% 18
0
1
2
3
4
5
6
7
8
9
0 2 4 6 8 10 12 14 16 18 20
ZSM-5 crystal, wt%
p
r
o
p
y
l
e
n
e

y
i
e
l
d
,

w
t
%
Decreasing base catalyst
HTI
FIG. 5. propylene yield vs. ZSM-5 crystal.

C
3
=
l
o
g

(
1

+

%
Z
S
M
-
5
)
R
2
= 0.95
1.0
1.5
2.0
2.5
3.0
3.5
0.26 0.28 0.30 0.32 0.34 0.36 0.38 0.40
Base catalyst HTI at 72 wt% conversion
SCT-RT test data, resid
FIG. 6. Base catalyst HTI influences propylene yield shift.
Clean Fuels
catalyst architecture with unsurpassed high mass transfer or dif-
fusion character, tantamount to the highest catalyst accessibility.
Another method of reducing HT is to produce catalyst par-
ticles with a highly accessible pore structure that allows very
rapid diffusion of oil molecules in and out of the catalyst par-
ticle. A high accessibility catalyst allows the olefinic products
of primary cracking to escape from the catalyst particle more
quickly. HT is a bimolecular reaction that requires the reactants
to be in close proximity of a pair of acid sites; so, by reducing the
residence time of olefins within the catalyst particle, the rate of
HT is reduced.
A second benefit of high accessibility is increased preser-
vation of primary cracking products. This reduces liquefied
petroleum gas (LPG) selectivity but increases LPG and gaso-
line olefinicity. In a constrained system more LPG can then be
produced by tailoring the zeolites, including those designed for
propylene production, used in the catalyst.
One companys worldwide equilibrium catalyst database
shows a clear example of the effect that high catalyst accessi-
bility technology has upon HTI. The company routinely tests
equilibrium catalysts (Ecats) collected from FCC units all over
the world in a standard micro reactor test called the fluid simu-
lation test (FST). This test is conducted with constant feed
quality and reaction conditions, and allows direct comparison
of catalyst yield selectivity. This companys high accessibility
catalyst technology exhibits a lower HTI compared to two ma-
jor competitive catalyst technologies, as illustrated in FIG. 7.
Based on these principles, the company developed a maxi-
mum propylene catalyst (MPC). The MPC is a new concept in
FCC catalyst design specifically developed for operation at high
propylene yield. A unique feature is the high accessibility struc-
ture used to reduce HT relative to conventional FCC catalysts at
the same RE level. The FST test data in FIG. 8 illustrates reduc-
tion in HTI that is achieved by high accessibility compared to
equivalent formulations prepared using a conventional low ac-
cessibility technology.
For VGO applications, the additional reduction in HT allows
maximum preservation of gasoline olefins for cracking to smaller
olefins, delivering the highest possible propylene yield.
In residue FCC, maximization of propylene poses addi-
tional challenges. To maximize propylene a low zeolite UCS
is required, and this is achieved by reducing RE. However, at
the higher levels of contaminant metals found in residue FCC
operation, some RE is necessary to stabilize the zeolite crystal
structure and provide resistance against deactivation by vana-
dium and sodium. The reduction in HT obtained from high
catalyst accessibility means that RE can be higher, providing
an activity advantage compared to a low accessibility product.
A critical aspect in the maximum propylene FCC catalyst
design for residue FCC is an optimization between minimizing
HTI for maximum propylene and retaining sufficient activity
for acceptable catalyst consumption and conversion, at an op-
timized RE level.
The maximum propylene yield is closely correlated to the
inherent HT activity of the catalyst. Zeolite stability begins to
decline more rapidly than the HTI index as the RE content of
zeolite approaches zero. The activity advantage provided by
high catalyst accessibility increases as the target propylene yield
also increases, as additional zeolite can be added to the cata-
lyst particle to compensate. As the propylene target increases
and the design HTI decreases, a maximum zeolite constraint is
reached, and the activity advantage provided by a high acces-
sibility structure increases rapidly (FIG. 9).
0.15
0.20
0.25
0.30
0.35
0.40
60 62 64 66 68 70 72 74 76 78 80
Ecat FST conversion, wt%
E
c
a
t

H
T
I
MPC catalyst
Competitor A
Competitor B
FIG. 7. HTI of various catalyst technology platforms.
0.10
0.15
0.20
0.25
0.30
0
RE on zeolite
H
T
I
Low accessibility
High accessibility
Max
FIG. 8. High accessibility reduces HTI.
TABLE 6. AFX applications demonstrated
RxT Rx-Press SG API S CCR Ni V C
3
=
RFCC-1 543 1.4 0.931 20.6 0.38 4.7 4.7 9 10.5
RFCC-2 528 1.7 0.921 22.1 0.32 3.9 4.4 6.7 9
RFCC-3 545 1.8 0.912 23.5 0.3 4.4 8.4 2.2 10.5
RFCC-4 544 1.4 0.93 20.5 0.5 6.0 10 10 10.8
FCC-1 545 2.5 0.899 25.8 0.1 0.1 11.8
FCC-2 555 2.6 0.908 24.3 0.16 0.1 10.7
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.12 0.16 0.20 0.24 0.28 0.32
Hydrogen transfer index
R
e
l
a
t
i
v
e

z
e
o
l
i
t
e

a
c
t
i
v
i
t
y
High accessibility
Low accessibility
Increasing propylene
24% higher relative activity
81% higher relative activity
FIG. 9. Activity advantage of high accessibility increases with
propylene yield.
Clean Fuels
Maximum propylene applications in practice. Laboratory
evaluations have confirmed the understanding of the complex
and competing reactions involved in propylene maximization.
Many customer laboratories have tested MPCs from multiple
suppliers in several applications, ranging from very light feed-
stocks to heavy residues. Tests have been conducted at pilot
scale as well as bench scale. One example of a very clean feed
application is illustrated in FIG. 10, where a third party bench-
marked five competitive MPCs. It confirmed superior propyl-
ene yield of the high accessibility, low HT MPC catalyst.
MPCs are preferred for challenging applications at or close
to the plateau level of propylene, in high pressure operations
and in resid FCC units processing heavy residue. They are also
preferred for grassroots modern FCC units, which are all in
some way operating on the edge of what is possible.
LITERATURE CITED
1
Greensfelder, B. S., et. al, Ind. Eng. Chem: 41:2573, 1949.
2
Feignet, F., Echard, M., and T. Gauthier, Pilot plant testing for resid to propylene,
8th FCC Forum.
3
Nieskens, M., et. al, The assessment of carbenium-ion and radical cracking in fluid
catalytic cracking, Akzo Workshop: The MON of FCC naphtha, 1987.
4
Venuto, P. B. and E. T. Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel
Dekker, New York, 1979.
5
Letzsch, W. S., Petrochemical building blocks from heavy oils PTQ, Summer 1999.
6
Maadhah, A., Integrating refining and petrochemicals, Hydrocarbon Engineering,
June 2003.
7
Angevine, P. J., Zeolites to Maximize FCC Olefins, Technology, Licensing and
Commercialization, ChemIndix 2007, SPS/05.
8
Plain, C., R2R (RDS-RFCC): The Ideal Partnership, BBTC, Barcelona 2008.
9
Lappas, A. A., et. al, Production of liquid biofuels in an FCC pilot plant using
waxes produced from biomass to liquid process, Ind. Eng. Chem, 2011.
10
Yung, Y. and K. Bruno, Low RE catalysts for FCC operations, PTQ,
Q1 2012.
11
Arriaga, R. and K. Bruno, Applying low RE technology in demanding FCC opera-
tion, NPRA Annual Meeting, March 2012, San Diego, California.
12
Bruno, K. and Y. Yung, Choosing the advanced option, Hydrocarbon Engineering,
September 2010.
CAREL POUWELS graduated as a chemical engineer from Delft University
of Technology in 1987. Upon graduation, Mr. Pouwels joined Albemarle in its
application research division. He now serves as the companys global FCC specialist
for resid applications.
KEN BRUNO received his PhD in chemical engineering from the University of
Notre Dame. He is Albemarles global applications technology manager for FCC.
8
9
10
11
12
13
14
74 76 78 80 82 84 86
Conversion, wt%
P
r
o
p
y
l
e
n
e
,

w
t
%
MPC technology
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Website
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Website
ADIPEC ..........................................................105
Avondale ........................................................ 74 (77)
www.info.hotims.com/45677-77
Axens ..........................................................C-80 (51)
Axens .............................................................112 (53)
Bartec GmbH ...................................................13 (153)
BASF Corporation ......................................... C-82 (70)
Cat Tech International Ltd ............................. C-76 (64)
Cat Tech International Ltd .............................C-94 (65)
Criterion Catalyst & Technologies, L.P. ............ C-84 (55)
Cudd Energy Services ...................................... 28 (158)
Curtiss Wright Flow Control Co., TapcoEnpro ...... 53 (67)
Dresser-Rand ...................................................13 (155)
Emerson Process Management (DetalV) .............14 (63)
Emerson Process Management (Fisher) ............ 27
Flexitallic LP ..................................................... 5 (93)
Foundation Fieldbus ........................................ 32 (159)
GE Measurement & Control ............................... 26 (157)
Grace Davison .............................................. C-86 (76)
Gulf Publishing Company
Construction Boxscore.................................... 49
EventsEMGC ............................................. 67
EventsIRPC .............................................1819
HPI Market Data 2013 ....................................104
Marketplace ..........................................106108
Haldor Topsoe A/S ........................................ C-88 (103)
Heat Transfer Research Inc. .............................. 30 (57)
Hydro, Inc. ...................................................... 20 (72)
Hytorc ............................................................ 73 (162)
Inprocess Technology Consulting Group S.L. .......12 (151)
ITW Polymer Technologies / Chockfast .............. 48 (160)
Linde Process Plants ........................................ 33 (85)
Merichem Company ......................................... 20 (84)
Paharpur Cooling Towers, Ltd. .......................... 24 (102)
PCC Energy Group ............................................ 70 (90)
Quest Integrity Group LLC..................................17 (156)
Rentech Boiler .................................................. 2 (82)
Sabin Metals Corporation ..............................C-90 (68)
Saint-Gobain Norpro .................................... C-92 (80)
Samson GmbH ................................................ 63 (161)
Sandvik Materials Technology .......................... 50 (61)
Spraying Systems Co ....................................... 10 (66)
Summit Industrial Products, Inc. .......................12 (152)
Tiger Tower......................................................61 (75)
Trachte USA .....................................................13 (154)
UOP LLC .....................................................29, 111
ZymeFlow Decon Technology ........................... 64 (92)
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Engineering
Case Histories
A. SOFRONAS, CONSULTING ENGINEER
http://mechanicalengineeringhelp.com
Case 71: Statistical visual data can be useful
in troubleshootingPart 2
In Case 71: Statistical visual data can be useful in trouble-
shootingPart 1, the editorial focused on how taking data and
analyzing it could determine the cause for high reject rates. Poor
fixture maintenance and torque control were major contributors.
Lets assume that the facilitys management would not allow
the production line to shut down for data collection. Only the
drawing details were available to the engineers. These drawings
were of the clamping fixture holding the part, which was essen-
tially a screwwedge arrangement. In this case, analytical mod-
eling would be useful for determining possible root causes. This
approach would allow the maintenance department to antici-
pate needed work to be included in the next planned downtime.
The screw has torque applied to it by the hydraulic motor,
and the cam wedge clamps the part into place. With too much
force, the part will distort; with too little force, it will move and
cause machining errors. FIG. 1 shows a very simplistic model of
this clamping fixture.
When torque is applied to the bronze nut by the hydrau-
lic motor, the screw moves up or down, , forcing the cam ac-
tion. This symbolically represents the mechanism that applies
force to secure the part for machining. This model contains the
clamping force, F
x
, the applied torque, T, and the friction coef-
ficients, , between the various cam, thread and wedge surfaces,
which are not shown. With this information and some basic
screw thread geometry and theory, an analytical model can be
developed. After some mathematical gymnastics, the equation
relating the clamping force to the applied torque is:
F
x
/ T = { [ r tan( + ) + r
c
] [cos sin + cos
2
] }
1
where = tan
1
and is the friction coefficient between all
surfaces
= tan
1
[ 1 / t ) and t is screw threads/in.
With the geometry known, FIG. 2 can be constructed. FIG.
2 confirms what was determined by the 216 tests. With poor
maintenance, the clamping force will vary greatly. With T = 300
in.-lb, the clamping force could vary from 5,100 lb to 9,600 lb,
depending on the condition of the fixture, with the friction co-
efficient limits assumed.
Since testing indicated a scatter of 1,000 lb to 6,000 lb, some-
thing else is also occurring. Testing indicated that the coefficient
of friction could vary considerably from the assumed textbook
values and also that some worn torquing devices produce much
less torque than predicted. For example, with = 0.3 and T=
200 in.-lb then F
x
1,300 lb.
The model alone, without testing, would have had the in-
vestigation proceed in the correct direction and away from the
speculation that the measuring method or machining techniques
were the cause. Plans could then be made to take test data as was
done in Case 71. Since the production line was down for a model
changeover, time for testing was available for data collection.
End of series. Part 1, November 2012.
DR. TONY SOFRONAS, P.E., was worldwide lead
mechanical engineer for ExxonMobil Chemicals before
retiring. He now owns Engineered Products, which
provides consulting and engineering seminars on
machinery and pressure vessels. Dr. Sofronas has
authored two engineering books and numerous
technical articles on analytical methods. Early in his
career, he worked for General Electric and Bendix, and
has extensive knowledge of design and failure analysis
for various types of equipment.
Clamping force, lb
F
x
Cam surface
Cam angle
Bearing
Bronze
nut
T, in.-lb
r
r
c
FIG. 1. Model for determining the effects of friction and torque.
0.00 0.05 0.10 0.15 0.20
10
20
40
30
Coefcient of friction,
F
x
/
T
Poor
nish
Good nish
Probable range
FIG. 2. Effects of poor lubrication and cam finish.
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