REFINING DEVELOPMENTS SPECIALREPORT

Achieve success in
gasoline hydrotreating
Case history describes achieving top performance
in FCC gasoline hydrotreater
K. SANGHAVI, Alon USA, Big Spring, Texas; and
J. SCHMIDT, Axens North America, Inc., Houston, Texas

S
uperior FCC gasoline hydrotreating performance is achiev- The PC believed that it can all be done by working with a lot
able by selecting the optimal process scheme to minimize of due diligence and fiduciary responsibility and selecting a game-
octane loss. Enlisting help from a refinery process consultant changer FCC gasoline hydrotreating process as well as selective
(PC) and technology licensor and collaborating early in the design hydrodesulfurization catalyst. This task was even more difficult
stage, further ensures the success in determining the better design at BSR as:
for the facility. Consequently, maintaining cost-effective solutions The refinery has the worlds shortest FCC main fractionator,
for a staged project investment and operating the worlds short- at only 61 ft in height with 15 trays and two packed-bed sections.
est FCC main fractionator subjected Alon Big Spring Refinery Thus, the FCC gasoline can have some heavy and tough-to-treat
(BSR) with difficult project challenges. The roadmap used for a sulfur compounds from the light cycle oil (LCO).
two-phase project and the lessons learned during Phase I (Interim The semi-regen reformer is the refinerys sole source for
Case) contributed to the successful implementation of Phase II hydrogen, where hydrogen purity varies from 88.6% at start of
(Ultimate Case). By knowing the key process and operational run to 74% at the end of the run. When reformer is down, hydro-
principals, the Alons Big Spring new hydrotreater yields world gen purity from purchased liquid hydrogen is 99.9%.
class performance with an excellent economic advantage.
FCC hydrodesulfurization principles. The key to treating
Case history. In early 2002, Alon, being an owner of a single FCC gasoline is in the ability to achieve the required sulfur reduc-
refinery in Big Spring, Texas, was granted the status of a small tion while maintaining octane levels. Octane loss results from
refiner and was initially required to reduce sulfur (S) in refinerys hydrosaturation of olefins in the feed during hydrodesulfurization
gasoline pool to less than 300 ppm between 20042009 (Interim (HDS) of thiophenes and benzothiophenes in FCC gasoline in
Case) and thereafter the refinery had to meet EPAs ultimate several steps. Both reactions occur in parallel and are shown here:
requirement of less than 30 ppm S (Ultimate Case). Typically, the Olefin + Hydrogen r Paraffin
refinerys PC would initially lead all process aspects of such a major Example: 4-Methyl -2-pentene +H2 r 2-Methyl-pentane
project such as determining the process design basis including, Thiophene + Hydrogen r Butane + H2S
feed analysis, selecting processing scheme and/or process licensor
and setting process scope. Early evaluations revealed that treating Fig. 1 shows the olefins and sulfur distribution in BSRs FCC
FCC gasoline would be the most optimal investment solution for gasoline, with the highest amount of olefins and lowest sulfur
the BSR. Of the five different processing schemes available at the occurring in the front end. Table 1 lists the octane numbers for
time, the initial study narrowed down the list to three processes for
further study. Then BSR acquired access to an idle 6,000 bpd (6 TABLE 1. Octane number of olefins and saturated
Mbpd) straight-run (SR) naphtha hydrotreater (NHT) complete paraffins
with a recycle compressor from an adjacent idle reformer. Octane numbers RON MON
Consequently, the refinery management asked the PC these
1-Pentene C5 olefin 91 77
questions loaded with monumental challenges:
2-Methyl-2-butene C5 olefin 97 85
a) Can we relocate and revamp the acquired idle equipment
sized for only 6 Mbpd of SR naphtha to a 13.8 Mbpd unit treat- n-Pentane C5 paraffin 62 62
ing FCC gasoline rich with 36 vol% olefins? 3-Methyl-2-pentene C6 olefin 97 81
b) Can we decrease FCC gasoline sulfur from 3,000 ppm to 4-Methyl-2-pentene C6 olefin 99 84
30 ppm with enviably limited octane loss? n-Hexane C6 paraffin 25 26
c) Can we do all this with an intermediate operation (Interim 2,2,4-Trimethyl-1-pentene C8 olefin > 100 86
Case) with undercut FCC gasoline with 1,650 ppm S1,700 ppm
2,2,4-Trimethyl-2 pentene C8 olefin > 100 86
S and achieve 90% sulfur reduction, to differ capital expenditure
and thus utilize the advantage of being a small refiner? n-octane C8 paraffin Minus 19 Minus 15

HYDROCARBON PROCESSING SEPTEMBER 2011

I 59
 REFINING DEVELOPMENTS SPECIALREPORT

FCC) was used. It required several startup issues to be resolved effectively resolved with installing feed filters, SHU and macro-
and incorporated into the final startup procedures. Additionally, porous media to the HDS reactor grading system, as evidenced by
BSR provided detailed training to operations, technical support pressure drop charts for both SHU and HDS reactor, as shown in
and maintenance outlining the finalized procedures. Color-coded
process flow diagrams for each step with associated operating TABLE 3. Revised equipment sizes for greater flexibility
parameters were used in training. The diagrams as part of the
training contributed to the successful start-up. Base case Alternative cases
Purity case average Low High
Results. Post startup audit and an outside review have revealed Makeup H2 purity, % 80.2 74.0 88.6
that this unit: 1) meets the BSR gasoline pool sulfur specifica- Recycle gas, MW 8.4 10.56 3.07
tions of 30 ppm S and 2) has the best performance amongst Reciprocating compressor, acfm 1,320 1,320
other similar functional competitors units, achieving very low H2 flow, lb/hr 17,758 22,257 6,678
octane losses in a single-stage unit when processing feed with SHU reactor steam preheater,2 ft 260 603
high olefin and high sulfur, nominally at 2,1002,400 ppm S,
HDS reactor effluent air cooler, MMBtu/hr 22 42.3
as shown in Fig. 7.
The refinery has experienced enviable octane losses as low as H2 heater, MMBtu/hr 10.7 13.34
0.30.5. The refinery PC recently developed an excellent cor -
relation for predicting octane losses as a function of feedrate and
4,500 4.5
% HDS. This helps BSR manage octane losses in the range of 4,000 4.0

Feed sulfur, wppm

Feed sulfur (R+M)/2 loss
0.70.8 at normal feedrates with 2,300 ppm S and 97.2 % HDS. 3,500 3.5

(R+M)/2, loss
3,000 3.0
Most other typical FCC gasoline hydroprocesses treat feed with 2,500 2.5
less than 1,300 ppm S and while % HDS is typically less severe, 2,000 2.0
at less than 96.1%, and still experience octane losses commonly 1,500 1.5
1,000 1.0
in the range of 1.41.5 or higher. On this basis, BSR has reached 500 0.5
top of the class in FCC gasoline hydrotreating. Higher S feeds at 0 0.0
BSR is directly due to processing of higher sulfur West Texas sour 0 50 100 150 200 250 300 350 400 450 500 550 600
Days since 1st startup
crude, providing BSR another great economic advantage over
refineries processing sweet crudes. FIG. 7 Feed sulfur and octane loss for Ultimate Case.
The issue related to high HDS reactor pressure drops has been

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65
 REFINING DEVELOPMENTS

FIG. 5 Example of coke buildup on catalyst and the

agglomeration from unstable dienes in feed.

3,500 3.5
3,000 Feed sulfur (R+M)/2 loss 3.0
2,500 2.5
Sulfur, wppm

(R+M)/2 loss

2,000 2.0
1,500 1.5
1,000 1.0
500 0.5
0 0.0
0 150 300 450 600 750 9001,0501,2001,3501,5001,6501,800
Days since 1st startup
FIG. 6 Feed sulfur and octane loss during the Interim operating
case while meeting 150-ppm S in gasoline.

Another unit re-design included a continuous wash-water

injection system due to the extra bay at the reactor effluent air-fin
condensers, which were susceptible to chlorides in the makeup
hydrogen. It also provided the option for a future water-wash
column to minimize amine carryover.

Startup of ultimate operation. In 2009, the BSR started

the revamped Ultimate Case. The successful startup was contrib-
uted to several key factors:
1) The technology licensor and BSR inspectors performed a
detailed conformance check of new vessels and trays. The SHU
and HDS reactor internals were a focal point to ensure proper
installation and levelness.
2) Safe loading of pre-sulfided, pre-activated catalyst, that
does not require in-situ sulfiding or activation step, was supervised
by catalysts provider/BSR verifying correct layers and loading
densities.
3) Combined efforts in writing detailed start-up procedures
and complete technical assistance during startup.
4) Around the clock technical support by technology licen-
sor and BSR technical engineers.
Modified startup procedures were necessary as BSR did not
have the typical feedstock (low olefinic naphtha) required for
startup. A more difficult feedstock (the normal feedstock from
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 REFINING DEVELOPMENTS SPECIALREPORT

the need for feed filters, feed pretreatment

LCN
with SHU and arsenic guard as a part of the product
grading system for the HDS reactor. Table 2 SHU reactor New equipment/pipin g-Phase 2
highlights the design feed characteristics for Ultimate
case feed Revamp equipmen t-Phase 2
the Interim and Ultimate Cases. Existing equipment/piping-Phase 1
BSR full-range FCC gasoline has a lon- F/E heat
Interim exchangers Splitter
ger end-point tail than normal due to its case feed Stripper
very short FCC main column. This material
was being undercut for the Interim Case F/E heat
Makeup H2
operation. When compared to typical FCC exchangers H2 heater
Recycle
naphtha feedstocks, the BSR feed proves to compressor
be one of the most difficult with high sul-
fur and olefin content. The concentration A/B/C D
of dienes, as measured by MAV analysis, is HDS reactor
Reboiler
Productseparator
exceptionally high and resulted in frequent
pressure drop buildup events during the
Interim Case. Effluent cooler Purge Amine HCN produc t
contactor
Despite the difficult feedstock processed
even during the Interim Case, the results
met BSR product sulfur specification with Wash water Liquid quenc
h
excellent octane retention. Fig. 6 highlights FIG. 3 Final process design for B SR FCC gasoline revamp.
the feed sulfur and (R+M)/2 octane loss
during the Interim Case while meeting the
150 ppm S gasoline pool specification. The
higher than design feed sulfur during the Interim Case was the 80
result of processing higher end-point material, a step closer to the
planned future ultimate case full-range feed. During this period, 60
there were refinery hydrogen limitations. To conserve hydrogen
ReactorP, psi

in the diesel hydrotreater, LCO make was reduced by increasing

the Interim Case gasoline end point. 40

New thinking for the ultimate operation. The ultra- 20

low-sulfur gasoline (ULSG) requirement of 30-ppm sulfur in the
gasoline pool was required by BSR starting after 2009. To meet 0
the regulation, the Interim operation was now set to be revamped 0 150 300 450 600 750 900 1,050 1,200 1,350 1,500 1,650 1,800
to the Ultimate operation. Not only was it necessary for the prod- Days since 1st startup
uct sulfur to meet requirements but also 1) excellent octane reten-
FIG. 4 Pressure drop due to buildup in the H DS reactor due to
tion to meet refinery economics and 2) a continuous catalyst cycle lack of pretreating feed.
to meet the four-year FCC turnaround schedule. Also during the
Interim operation, the BSR crude capacity increased thus rais-
ing the FCC gasoline rate. This required a new study to assess TABLE 2. Design feed characteristics for Interim and
the impact from a higher feedrate to the HDS section, from the Ultimate Cases
original Ultimate Case value of 8 Mbpd to 10.8 Mbpd. Feed properties Undercut full range, FCCN Full range, FCCN
A common industry practice is to design the units reactor and Sulfur, wppm 1,6501,700 3,0694,132
heat transfer equipment including the heater(s) based on a) both
Olefins, vol% 36.0 35.037.0
reactors being at the start of the run (SOR) and/or both reactors
being at the end of the run (EOR), in tandem, based on a four-year MAV, mg/g 1522 1221
run length and b) the average hydrogen purity at 80.2% for BSR. D-86, vol% F F
But during mid-2008 when restarting work for the Ultimate 10% 110120 114
Case to increase operational flexibility and economic advantage, 90% 310355
the refinerys PC asked that other scenarios be considered in the 95% 330375 415420
design and equipment to cover: FBP 380430 450475
a) Staggered reactor operation, with SHU reactor being at
SOR while HDS reactor continues to run its course and vice
versa, which de-couples the reactors Also the refinerys PC requested adding a macroporous trap-
b) Unit flexibility to cover the expected 74%88.6% hydro- ping media for scales as a part of the HDS reactor grading system
gen purity as the semi-regen reformer cycle progresses. and using wedges and pins in place of traditional nuts and bolts
This revised basis increased sizes for the HDS reactor and for reactor internals, for easier installation and removal. Addition-
the units heat exchange equipment, as well as the sizes of the ally, due to the arsenic measured on the catalyst during the Interim
hydrogen heater and reactor effluent air-fin condenser, as shown operation, a layer of arsenic trap was installed on top of the main
in Table 3. HDS catalyst bed.
HYDROCARBON PROCESSING SEPTEMBER 2011
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SPECIALREPORT REFINING DEVELOPMENTS

Selective hydrogenation principles. In the selected

80 scheme, for the Ultimate Case, the feed would be pretreated in a
Sulfur 60 selective hydrogenation unit (SHU) to convert lighter mercaptans
70 55
Olefins
Cumulative sulfur

60 50 and light sulfides to heavier sulfur species and also to saturate

Olefins, vol %
50 45 unstable dienes with no octane loss and minimal hydrogen con-
40
40 35 sumption. Dienes, unless removed through saturation, would
30 30 thermally decompose and agglomerate into a coke crust; thereby
20 25 accelerating pressure drop buildup in the downstream HDS reac-
20
10 15 tor. This would then shorten the units run length.
0 10 Pretreated feed would then be fractionated in a splitter to
100 125 150 175 200 225 250 275 300 325 350
Cut end point, F
remove about 29 vol% to 33 vol% of the feed as onspec LCG with
less than 30 ppm sulfur and rich in high-octane olefins.
FIG. 1 Cumulative sulfur and olefins distribution vs. cut-end point. In most cases, the balance of the feed stream, HCG, would be
hydrodesulfurized to reduce sulfur to below 30 ppm. LCG can be
blended back with HCG. Otherwise, if a separate storage sphere is
available, then the LCG can be segregated for blending flexibility.
LCN to pool, TAME or alky unit BSR chose the former option for LCG. Selectivity of the HDS
catalyst to minimize octane saturation while treating heavier sulfur
compounds in HCG would determine the total octane loss.

Challenges of the Interim Case. With the idle 6,000 bpd-

ULSG
olefins vs. resulting saturated paraffins. Fractionation upstream
of the HDS section is an attractive first step to concentrate the
olefin-rich light-cat gasoline (LCG) as a product and the sulfur-
rich heavy-cat gasoline (HCG) for hydrodesulfurization (HDS).
BSR focused on several essential characteristics and challenges
in selecting a successful process including:
Minimize octane loss. Gasoline is hydrodesulfurized selec-
tively and collateral damage that can occur through olefin satu-
ration is minimized; accordingly, the scheme achieves the total
lower octane loss.
Minimize hydrogen consumption per barrel of feed was
another important consideration for BSR. Olefin and aromatic
preservation is essential; otherwise, a large amount of hydrogen
would be used in saturating these compounds as compared to
desulfurizing them.
Retain excellent gasoline yield with no Rvp increases.
This is vital for maximizing product. This is attainable with mild
operating conditions that avoid cracking reactions,
Maintain catalyst cycle length inline with the FCC turn-
around schedule to avoid untimely blending issues due to off-
spec FCC gasoline.
Conserve total capital investment to cover both the
Interim and Ultimate Case operations.
Detailed evaluation showed that for BSR, the selected gasoline
hydrotreating processing scheme could meet all of the essential
characteristics for both the Interim and Ultimate requirements.
Fig. 2 outlines the basic process flow diagram.
SR naphtha hydrotreater available as part of the FCC gasoline
hydrotreater revamp, the first of many project challenges were pre-
sented. In combination with a minimal investment requirement
for the Interim Case, the challenges increased significantly. A joint
effort between BSR and licensor to develop a scheme was initi-
ated to not only minimize investment but to meet the required
HDS level with acceptable octane loss for both the Interim and
Ultimate Cases.
Roadmaps. BSR developed roadmaps for both Interim and
Ultimate Cases so that the least amount of equipment would be
wasteful during the transfer from the Interim to Ultimate process-
ing schemes. The licensor and BSR worked closely to arrive at the
final Interim and Ultimate cases that encompassed the project
challenges and requirements. For the Interim Case, a simpler ini-
tial flow scheme was developed to meet the immediate processing
requirements, while simultaneously considering future require-
ments for the Ultimate Case. Despite the challenges presented, the
design basis for each case was studied, and the technology licensor
provided BSR with the final process design package. Both cases
are shown in Fig. 3.
Lessons learned contributed to success. The Interim Opera-
tion during January 2004 to September 2009 was with full-range
gasoline feed to the HDS reactor without pretreatment by the
SHU. This operating mode provided an opportunity to study
features needed for optimal Ultimate Operation. Fig. 4 shows
that the pressure drop buildup in the HDS reactor during Interim
Operation determined the units run length. The high pressure
drop would require frequent outages to skim the top-bed cata-
lyst or a complete catalyst changeout. This was attributed to the
absence of SHU pretreating and the protection it offers to the
HDS reactor. The importance of installing an SHU reactor in
the Ultimate Case was further strengthened. With a 30-wppm S
gasoline pool requirement for the Ultimate Case, frequent unit
downtime would jeopardize refinery economics/blending.
Analysis of crusts from the reactor revealed high coke buildup
from thermal decomposition and agglomeration of unstable
dienes in the feed, as shown in Fig. 5. Also, the catalyst deactiva-
tion rate was high during the Interim Operation. Analyses done
on the spent catalysts revealed significant arsenic contamination
which was linked to the feed. The lessons learned confirmed

60
I SEPTEMBER 2011 HydrocarbonProcessing.com
 REFINING DEVELOPMENTS

20

Pressure drop, psi

16 SHU DP HDS DP

12
8
4
0
0 50 100 150 200 250 300 350 400 450 500 550 600
Days since 1st startup
FIG. 8 Pressure drop across the H DS and SHU.

TABLE 4. Ultimate operation HDS reactor performance

Time 10/23/2009 1/31/2011 5/30/2011
Day onstream 14 460 575
HCG feed, bpd 7,964 7,890 7,925
HCG HDS, % 99.0 98.1 98.5
Normalized P, psi 4.3 6.6 6.9
Deactivation rate < 0.5F/month

Fig. 8 and Table 4. The HDS reactor is almost close to start of run
temperature after one-half years of operation. The arsenic con -
tamination of HDS reactor seems to be effectively resolved too.

Successful project. BSR FCC gasoline HDS unit is in a

position to provide the refinery excellent economic advantage
and leverage. It has demonstrated that it will not constrain refin-
ery operations while processing lower-cost sour crude oils that
in turn results in feeds with higher sulfur. This can be classed as
an extraordinary achievement, especially for the worlds shortest
FCC main fractionator and restrictions imposed by repurposing
an idle 6 Mbpd NHT and reformer compressor. Intelligent factors
contributing to top of class performance are:
(1) Superior processing scheme, based on saturation of unsta-
ble dienes in a selective hydrogenation unit and separation of
the front-end FCC Gasoline as LCG before HCG is treated in
reactor with selective HDS catalyst. This scheme would always
assure process success in terms of superior octane retention and
four-year unit run length.
(2) Early roadmaps prepared for both Interim and Ultimate
Cases ensure minimal wastage of investment.
(3) Implementing lessons learned from the Interim Case into
Ultimate Case design resolved issues related to high reactor pres-
sure drops, catalyst activity, catalyst stability and catalyst arsenic
contamination.
(4) Excellent capability of the refinerys PC to guide the licen-
sor and also for setting right design basis and process direction and
infusing new thinking for a more robust unit. H P

Kirit Sanghavi is senior refinery process engineering consultant at Alons Big

Spring Refinery. He is responsible for the largest capital projects at this refinery. Previ -
ously, Mr. Sanghavi worked at Esso Chemical and Imperial Oil in Canada for 15 years
and for four Engineering Companies in the US, UK and Canada during his career. He
earned a bachelors degree in chemical engineering from London University.

Jeff Schmidt is a senior technical service engineer for Axens North America, Inc.
He has been with the company for the past five years and is responsible for start-up
and technical support for Axens licensed units. Previous to Axens, he worked at UOP
for five years. Mr. Schmidt holds a BS degree in mechanical engineering from the
University of Wisconsin-Madison.
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