Originally appeared in:

July 2013, pgs 61-64.

Used with permission.

Special Report Refinery of the Future

J. Zurlo, GE Water & Process Technologies,
The Woodlands, Texas

Optimize amine units and improve

refinery profitability
The alkanolamine system in a refinery, better known as the ery, a consistent approach can be applied to these systems to
amine unit, is used to remove hydrogen sulfide (H2S), carbon improve operations and performance. The main factors to im-
dioxide (CO2), and mercaptans (collectively referred to as acid proving amine system performance include:
gases) from process gas and liquid hydrocarbon streams. Amine 1. Define the operating conditions that are optimal for the
units are an essential part of the refinery operation to maintain refinery and amine unit configurations as well as the needs for
product quality and environmental compliance. Their impor- acid gas removal
tance is increasing as refinery feeds become more sour and 2. Establish an amine management program to assess cur-
refinery product sulfur limits are lowered. A poorly operated rent conditions and identify improvement opportunities in
amine unit can result in high amine losses, poor unit reliability, both operations and amine conditions
amine solution contamination, off-specification products, op- 3. Identify and implement any changes to the mechanical,
erating headaches, and increased operating costs to the refinery. operational, or chemical configuration that would provide sig-
Despite their importance, amine unit operations are often nificant improvement to operations.
not well understood or operated optimally. This is likely due to
several factors, including: Best practice operating conditions. Amine treatment units
Amineunitsenablearefinerytomakeaprofit,butdonot are fairly robust in nature and can still perform adequately when
directly produce a profitable product operated a fair margin from design conditions. However, amine
The various parts of an amine unit are typically spread operation often deviates significantly from optimum. Initiating
out across different operating units: lean amine solvent is typi- relatively small operating changes to move back toward opti-
cally pumped to absorber towers in the process units contain- mum operation can result in significant cost savings without
ing the production fluids, then rich amine is pumped back to any sacrifice in performance. An example is that many amine
the stripper tower for acid gas removal, so control of the entire units operate at a higher circulation rate than needed to meet
circuit is not straightforward product specifications. This may be to maintain a high safety
Manyrefineryamineunitsareoperatedwellbeyondtheir margin or in response to a transient upset condition where oper-
original design capacities ations have not been returned to normal settings. High circula-
Aminesystemsareoftenrobustenoughtomaintainrefin- tion rates use more energy to pump the amine solution; require
ery product quality, even when operating far from either origi- more steam energy in the stripper to heat more amine; and in-
nal design or best operating practices. crease tower liquid velocities, which increases foaming tenden-
Conversely, there are many benefits that can be realized by cy and amine loss through higher entrainment rates. Table 1
improving amine unit operations, such as: more consistent outlines several key operating guidelines by unit equipment
product quality, resulting in reduced frequency of event-driven type to help maintain optimum operation.
activities to blend off or re-treat episodic off-spec products; low-
er energy costs; reduced costs for filters, activated carbon and re- Amine management program. Another key aspect of suc-
placement amine; improved reliability, which lowers equipment cessfully operating an amine unit for optimal performance is a
replacement/repair costs; and improved operation of the sulfur good amine management program. This involves monitoring
plant by providing a more consistent feed quality to this unit. the condition of the amine solution and managing the feed qual-
Solomon Associates recently wrote that the worlds top per- ity, operating conditions, and the amine solvent itself to avoid
forming refineries, as measured by their semi-annual bench- issues associated with highly contaminated or degraded amine.
mark studies, consistently perform above average in several key An effective amine management program requires frequent
categories, including: operational availability, maintenance cost inspection and analysis of the amine solution at regular inter-
efficiency index, energy intensity index, and return on invest- vals. This starts with a simple observation of the lean amine sol-
ment.1 Improving operation of the amine unit can help to im- vent itself. The circulating solvent should be clear, bright, and
prove each of these factors. free of visible solids. Fig. 1 shows samples from three different
Although there are differences in the configuration, de- amine systems and highlights the range of visual condition in
mands and operation of almost every amine system in a refin- amine solvent. One can easily envision how the unit using the
HYDROCARBON PROCESSING July 2013
 Refinery of the Future
Table 1. Key operating guidelines by unit equipment type to help maintain optimum operation
Unit/Parameter
gas absorber towers
Inlet temperatureproduct or amine
Rich amine loading
Liquid / vapor velocities
Tower pressure
Bottoms level
Defoamer injection rate
liquid absorber towers
Inlet temperatureproduct or amine
Rich amine loading
Liquid/vapor velocities
Amine/product interface level
Tower Pressure
amine stripper (Regenerator)
Reboiler heat flux
Reflux ratio
Tower pressure
Bottoms level
Defoamer injection rate
Reflux water ammonium
bisulfide concentration
Rich amine flash drum/separators
Oil skimming rate
Residence time
Flash gas rate
Solvent filtration
Filter element micron rating
Carbon bed life
Lean amine filter bypass loop
flowrate
amine solvent
Heat stable amine salts (HSAS)
concentration
Heat stable salts concentration
HSAS neutralization rate/frequency
Amine concentration
Corrosion monitoring
Consequence if:
Too low/erratic
Foaming
Corrosion riskhigh amine circulation rates
Channelinglow acid gas absorption
Foaming/low acid gas absorption
Foaming
N/A
Emulsion control issues
Corrosion riskhigh amine circulation rates
Channelinglow acid gas absorption
Low contact timelow acid gas absorption
Low acid gas absorption
High lean amine loadinginsufficient acid gas
stripping
High amine loss
Foaming
Foaming
N/A
N/A
Fouling/foaming
Fouling/foamingpoor hydrocarbon removal,
separation chemical treatment required
Corrosion potentialhot rich section
Operating cost increasehigh filter change frequency
Amine degradation, feed contaminants high,
increased fouling potential
Insufficient particulate removal
N/A
High amine losshigh purge/makeup of
fresh solvent
N/A
Insufficient acid gas absorption, high energy costs
increased stripping requirements
Uncontrolled corrosionnot caught until unit
operations are affected
HYDROCARBON PROCESSING July 2013
Too high/building
Low acid gas absorption
Corrosion in hot rich section
Amine lossentrainment
Fouling
Fouling
Fouling, foaming, amine degradation, reduced
carbon bed life (product type dependent)
Low acid gas absorption
Corrosion in hot rich section
Amine lossentrainment
Amine lossentrainment
Fouling
Fouling, amine degradation, corrosion risk
High lean amine loadinginsufficient
acid gas stripping, increased energy demand
Fouling, high lean amine loading
insufficient acid gas stripping
Fouling
Fouling, foaming, amine degradation, reduced
carbon bed life (product type dependent)
Corrosion potential, fouling potential
High amine lossuncontrolled amine solvent
bleed, high nitrogen to waste treatment plant
High amine loss, flare gas/downstream issues
Foulinginsufficient particulate removal
N/A
Operating cost increasehigh filter change
frequency, low carbon bed efficiency
Corrosion potential, fouling potential,
insufficient acid gas absorption
Corrosion potential, fouling potential,
Insufficient acid gas absorption
Corrosion potential, fouling potential
Increased corrosionhigh rich amine loading,
foaming/emulsion
N/A
 Refinery of the Future

solvent on the right will have more operating issues than the Optimization case history. A refinery on the US Gulf Coast
unit using the solvent on the left. Please note also that rectify- was experiencing several issues in its amine unit operation.
ing an amine unit whose solvent condition has degraded to the These included:
state of the solvent on the right can take several weeks of active Excessivefoaminginthecontactortowers
management to bring the unit back to best practice conditions. Rapidfoulinginthelean/richheatexchangers
It pays to identify and correct issues with amine solvent condi- Upsetstothefluidcatalyticcrackingunit(FCCU)op-
tion early, and to act aggressively. eration related to emulsion issues in the liquid contactor
Leanandrichfiltersthatwerebeingchangedfourtosix
times per month due to rapid pressure drop increase
Highsteamusage.
An assessment of the unit operations was made, and several
changes were recommended to improve operations, including
changes to the operating conditions and treatment programs.
The refinery has estimated that the performance improve-
ments at the amine unit have resulted in operating cost savings
of over $550,000 annually in energy, maintenance avoidance,
and material operating expenses.
Actions were taken in a stepwise approach, both to determine
the system impact from the changes and to optimize operating
expenses. Although there were several areas that would benefit
from improvement, an immediate issue that was addressed was
the repeated upsets to the FCCU operation due to poor per-
Fig. 1. Samples from three different amine systems.
formance in the liquefied petroleum gas (LPG) liquid-liquid
amine contactor tower. Stable emulsions formed when the
amine and LPG were mixed in the contactor tower caused high
In addition to visual observation, a foam shake test amine losses through carryover, loss of tower operating control,
should be performed daily on the unit. This test involves par- and periods of LPG product not meeting H2S specification lim-
tially filling a clear jar or bottle with cool lean amine, shaking its. An emulsion breaker designed specifically for liquid-liquid
vigorously for several seconds, and then observ-
ing the foam height above the liquid and the time
it takes for the foam to dissipate (known as the Routine monitoring is essential for early
break time). An amine solvent in good condition
can form a foam layer, but this foam should dissi- detection of corrosion potential in the
pate in a few seconds. Longer break times indicate amine unit. Corrosion detection devices
that the amine solution is starting to accumulate
contaminants that can cause operating issues such can show where corrosion is taking place
as high amine losses from foaming, trouble meet- and allow for a plan to correct the problem
ing treated fluid specifications, and reduction in
amine unit treating capacity. prior to equipment failure.
Other daily monitoring should include amine
concentration, lean and rich amine loading, and
ammonium bisulfide concentration in the reflux drum of amine contactors was applied to the system, the stable emulsion
the amine stripper. was broken, and LPG operations returned to normal. The ap-
On a monthly basis (or quarterly for units that do not plication of this treatment was optimized over the next several
show high stress), the lean amine should be analyzed for sol- months, while the next phasechanges to the operation of the
ids, metals, and acid contamination levels. amine systemwas being implemented.
In addition to monitoring the solvent itself, monitoring Amine circulation rates and changes to several of the con-
the equipment associated with handling amine contamination tactor towers were modified to increase the concentration of
should be monitored and conditions recorded. Carbon filter acid gas absorbed in the circulating amine solvent, known as
bed life, filter change frequency, skim rate on the rich flash rich loading. Increasing rich loading improves operating effi-
drum/three-phase separator, and knockout drum liquid accu- ciency, but care must be taken to avoid an increase in corrosion
mulation rates should be tracked to detect signs of increased in the hot rich amine section of the amine unit. As illustrated in
contamination and/or amine degradation. Fig. 2, the rich loading was increased about 25% over the course
Finally, routine monitoring is essential for early detection of several months, from an average of 0.30 mol/mol to 0.38
of corrosion potential in the amine unit. Regular results from mol/mol. Please note the slight gap in the chart data is due to a
corrosion detection devices can show when and where corro- maintenanceturnaroundinMarch2012.
sion is taking place and allow for a targeted action plan to cor- Analysis of filter elements and deposits collected in the unit
rect the problem prior to equipment failure and/or premature identified that corrosion byproducts, degraded amine, and high
unit outage due to reliability issues. silica in the amine unit were the main contributors to equipment
HYDROCARBON PROCESSING July 2013
 Refinery of the Future

0.700
Reducing system corrosion has also had the benefit of sig-
0.600 nificantly reducing filter change frequency, from four to six
0.500
times per month to once per month (Fig. 4). Each rapid drop
in pressure represents a filter change. Filter change frequency
Rich load, mol/mol

0.400 is now being held at once per month by procedure, not by

0.300 pressure drop limitation. This is illustrated by noting that the
pressure spikes on the chart are much lower than in the past.
0.200 The filter elements are being changed according to the calen-
0.100 dar, not the pressure drop.
0.000
20112012 data 14
Fig. 2. The rich loading was increased about 25% over the course 12
of several months.
10

Lean amine filter P, psi

fouling. Specifically impacted were the lean/rich heat exchanger, 8
the filter elements, and the stripper tower reboiler, which led to 6
high steam requirements to maintain stripper tower operation.
Further investigation showed that this refiner was using a 4
silicone-based defoamer to combat the frequent foaming events 2
in the contactor towers. While this type of product can be ef-
0
fective, overuse can result in foam stabilization and contribute 20112012 data
to system fouling. This defoamer was replaced with a non-sili-
cone product to address the negative effects of high defoamer Fig. 4. Filter change frequency was reduced from four to six times
demand while the root cause, system corrosion, was addressed. per month to once per month.
A short maintenance outage was taken to clean the heat ex-
change equipment in the amine unit and to prepare the unit
for application of an amine system corrosion inhibitor. Perfor- Improve reliability. Amine units are an essential unit opera-
mance of the system was assessed after the outage, and it was tion to maintain product specification and to safely handle
determined that steam use in the stripper reboiler was reduced the acid gases in the refinery operation. Attention to oper-
by about 27% (Fig. 3). Improving corrosion control in the sys- ating parameters, amine system conditions and performance
tem allowed the gains realized from cleaning to be maintained. can minimize operating costs and improve refinery unit reli-
60
ability and operations.

50
Jeffrey A. Zurlo is a senior strategic projects manager for GE Water &
Process Technologies. He has 22 years of experience in process engineering,
40
Steam ratio, lb/bbl

refinery treatment sales and services, hydrocarbon product applications and

technical support. Mr. Zurlo provides global technical support to the refining
30 industry, with a principal focus on best practices, and amine sweetening
programs. He began his career with GE in 1997 and holds a BE degree in
20 chemical engineering.

10 Acknowledgments
TheauthorwouldliketothankMichaelBloss,PatricioAyala,andChadAshman
0
for their contributions to this article.
20112012 data

Fig. 3. After the outage, steam use in the stripper reboiler was lIteRAtURe cIted
reduced by about 27%. 1
Proops, K., Worlds best refineries, Fuel,March2013.

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