AMINE PLANT TROUBLESHOOTING AND OPTIMIZATION:

A PRACTICAL OPERATING GUIDE

R.G.F. Abry
Dow Chemical Canada, Inc.
GAS/SPEC Technology Group
Ft. Saskatchewan, Alberta

M.S. DuPart
Dow Chemical U.S.A.
GAS/SPEC Technology Group
Freeport, Texas

Presented at:

1993 LAURANCE REID

GAS CONDITIONING CONFERENCE
Norman, Oklahoma
March 1 - 3, 1993

ABSTRACT

In today's gas treating industry, tighter operating margins mean that safe, continuous and
optimized amine plant operations are critical to a company's long term success. Effective
resolution of amine unit upsets along with continuous amine plant operations, where
operating and maintenance costs are at a minimum, play a large part in this success. These
considerations are as important in plants using generic amines such as monoethanolamine
(MEA) and diethanolamine (DEA) as in facilities using specialty amines based on
methyldiethanolamine (MDEA) and generic MDEA.

If approached properly, plant upsets can be handled effectively and quickly. A systematic
method for handling plant upsets will be discussed. These concepts are applicable to all
classes of amines. In the case of smoothly operating plants, procedures for optimizing will
be detailed.
INTRODUCTION

In today's extremely competitive and uncertain business climate, it is important that amine
plant operators maintain safe, continuous and optimized plant operations for both short and
long term success. Effective and fast resolution of amine unit upsets also play a large part in
this success. Regardless of the type of amine utilized, these considerations are important.
The key to both troubleshooting and optimization is a systematic approach. This paper w ill
attempt to give plant operators and engineers a template for a systematic method for
optimization and troubleshooting that will result in a more trouble free, continuous
operation.

DATA COLLECTION

Successful amine plant troubleshooting and optimization relies on reliable data collection and
interpretation. Because complete data collection is so important when troubleshooting or
optimizing an amine plant, the information listed in Figure 1 is the minimum amount of data
that should be collected on a routine basis. Frequently these items are collected as part of the
operators daily log. Items that are missing should be added to the daily log.

It is critical that data be collected during or at routine operating conditions when the plant is
running successfully. Without this baseline information, future operational optimization and
troubleshooting will be difficult and time consuming in addition to being "shots in the dark".
ALL UPSETS CAN BE TRACED BACK TO A CHANGE IN THE PROCESS. Identifying
and responding quickly to changes in the process w ill result in fewer upsets and a more
efficient plant operation.

It is worthwhile for operators / engineers to translate the information gathered in the log to a
graphical format for ease in tracking trends and identifying problem areas. These graphs will
become the control charts for the process and serve as a visual reminder of where the plant is
comfortably operated and if the process has changed or is drifting away from the norm.

TROUBLESHOOTING

Troubleshooting of amine plants usually falls into four categories:

1) Failure to meet specification

2) Foaming
3) Amine losses
4) Corrosion

The first two categories; failure to meet specification and foaming, are normally immediate
concerns requiring quick action, while the latter two categories; amine losses and corrosion,
are longer term in their manifestation. A discussion of the four troubleshooting categories
follow.
Failure To Meet Specification

As outlined in Table 1, failure to meet the treated gas specification can be the result of a
single factor or several factors working in conjunction with each other. Generally, it is a
process of elimination that results in final identification of the problem. The faster possible
contributing factors can be ruled out, the quicker the problem can be identified and
corrected. By monitoring key process parameters that could result in off specification treated
gas and responding appropriately before they become a concern, the problem can sometimes
be avoided all together.

As suggested by Table 1, key process parameters that should be monitored and graphed
would be lean amine temperature, lean amine concentration, lean H 2 S and/or C02 loading,
amine circulation rate, stripper overhead temperature, absorber delta P, inlet gas flow, inlet
gas H 2 S and/or C02 concentration and of course the treated gas composition. A prior
knowledge of anticipated conditions and operating ranges and the effect these parameters
will have on the treated gas specification are helpful in setting control points and
appropriately reacting to changes as observed on the control charts. A proactive approach to
plant operations is always better than a reactive one.

Lets take for example a plant designed to treat 15 MMSCFD at 500 psia and 100 Deg F that
contains 3% C02 and 5% H2 S down to < 4 ppm H 2 S and 2% maximum C02 with a 50 wt%
MDEA solution at 100 8pm. In this case, knowledge of trends that would be useful in
setting up control charts and ranges might include, but are not limited to, H2 S in treated gas
vs. lean H 2 S loading, H 2 S in treated gas vs. lean amine temperature, stripper overhead
temperature vs. reflux ratio, lean H2 S loading vs. stripper reflux ratio, and turn up and turn
down characteristics of the tower at different circulation rates (see Figures 2 -6). Knowing
directionally which way the plant will respond under different conditions, allows the
operators to respond quickly and in an appropriate manner to upset or changing conditions.
Similar curves can be easily generated for different amines and process conditions.

Figure 7 is an example of how a control chart might be used for the above case. In this
example the plant is performing adequately and meeting specification until finally the H2 S
goes out of specification. Without the control chart the operator would not know that the
plant was heading for trouble and when it finally went off spec, would be in a panic
situation. However, by plotting the data it becomes obvious that the H2 S is creeping up and
is due to the lean H2 S loading going up at the same time, probably due to a problem in the
stripper as indicated by the corresponding decrease in the stripper overhead temperature.
This example is simplistic, but points out the power of control charts combined with a little
process know how.

Foaming

Foaming is the most common cause of upsets in an amine plant, usually resulting in
excessive amine losses, off specification treated gas and a reduction in treating capacity,
all of which effect operating costs and revenue. Listed in Table 2 are some of the common
symptoms of foaming along with likely causes. Monitoring key parameters such as absorber
or stripper pressure drop, vessel liquid levels and treated gas outlet composition can alert the
operators to potential foaming problems.

Figure 8 illustrates the use of a control chart to alert the operator to a foaming problem by
monitoring absorber delta P. Again, not only is it important to monitor key process
parameters, but to understand what they are indicating so appropriate corrective or
preventative action can be taken.

The operating philosophy when dealing with foaming should be to address the root cause of
the foaming as opposed to continually treating symptoms. Use of antifoams for temporary
relief from foaming is acceptable, but for longer term, more reliable operation, identifying
and correcting the root cause(s) should be the norm.

Amine Losses

Every amine plant can expect to have some amine losses associated with its operation and
acceptable losses will vary from application to application. However, excessive amine losses
can have a negative economic impact on the total operating cost of a plant and it is important
to understand how losses can occur and the appropriate corrective action to take. Losses
usually fall into five major categories: mechanical, entrainment, solubility, vaporization and
degradation. Listed in Table 3 is a troubleshooting guide for amine losses based on Stewart
and Lannings' 1991 GCC paper 1 that the amine plant operator or engineer should find
useful.

Corrosion

Corrosion in amine units can result in unscheduled down time, loss of production, reduction
in equipment life and even injury or death. Corrosion in alkanolamine gas treating plants can,
however, be controlled and minimized with proper plant design and operating parameters.
The key is to minimize acid gas flashing and to understand other contributing factors that can
enhance corrosivity of amine solutions. Like the three previous categories, monitoring and
an understanding of key process parameters can help minimize corrosion in amine units.
Listed in Table 4 is a troubleshooting guide for corrosion that is based on DuPart, Bacon and
Edwards' 1991 GCC paper 2 that again the amine plant operator or engineer should find
useful.

OPTIMIZATION

With today's tight margins and uncertain economic climate in the gas industry, it is almost
imperative that amine plant operations be optimized to the maximum. It is no longer going to
be acceptable to operate plants with huge safety margins on circulation rate and energy input.
Plants will be required to function closer to the edge of the operating envelope. This new
operating discipline can only be achieved with an
understanding of the operating envelope and the penalties associated with huge safety
margins.

To successfully optimize an amine unit and maintain the process in an optimized state, a
good baseline data set and an understanding of and a commitment to optimized target
conditions is required. If one or the other is missing, the optimization will be haphazard or
will not occur. Again, the continuous gathering of plant data, graphical representation of the
data on control charts and an understanding of the cause and effect relationship between
different process parameters is a key aspect of successful plant optimization.

An important aspect of plant optimization, but frequently overlooked, is to get everybody

involved in the process. Teamwork and "buy-in" are very important and will contribute to
short and long term success.

Optimization of a plant entails the correct balance between capacity, energy and corrosion.
Ideally, the quantity of acid gas in the treated gas stream should be slightly less than the
maximum specified limit, the heat input to the reboiler should be at a minimum and
corrosion should be within tolerable and accepted limits.

Outlined below and in the following example is a format that has proved to be successful in
optimizing amine plants.

1) Gather and examine baseline data set

2) Identify potential areas for improvement
3) Set target process parameters
4) Adjust target process parameters
5) Monitor changes in process as result of adjustments
6) Determine leading edge process parameters
7) Record and visibly display optimized / leading edge process parameters
8) Calculate $ savings and communicate to anyone that will listen

Example

Lets take a plant that was originally designed for 50 MMSCFD, but due to declining flows
from the field is only treating 30 MMSCFD.

DESIGN CURRENT BASELINE

Inlet Gas Flow, MMSCFD 50 30

Inlet Gas Pressure, psia 1000 850
Inlet Gas Temperature, Deg F 100 100
Inlet H2 S, mole% 7.0 7.0
Inlet C02 , mole% 3.0 3.0
C02 Specification, mole% 2.0 MAX 2.0 MAX
C02 In Treated Gas, mole% 1.47 1.13
H2 S Specification, ppm <4 <4
H2 S In Treated Gas, ppm 2.40 0.54
Example Continued
DESIGN CURRENT BASELINE

Wt% MDEA 50.0 40.0

Amine Circulation, 8pm 440 350
Lean H2 S Loading, mole/mole 0.005 0.002
Rich H2 S Loading, mole/mole 0.409 0.385
Lean C02 Loading, mole/mole 0.005 0.002
Rich C02 Loading, mole/mole 0.101 0.110
Lean Amine Temperature, Deg F 110 110
Rich Amine Temperature, Deg F 150 141
Rich Amine Entering Stripper, Deg F 217 217
Stripper Overhead Temperature, Deg F 206 213
Stripper Reflux Ratio, mole/mole 1.20 2.00
Stripper Bottoms Temperature, DegF 247 245
Stripper Bottoms Pressure, psig 10.0 10.0
Inlet Temperature to LA Cooler, Deg F 178 167
Reboiler Duty, MMBtu/hr 24.93 20.94
X-Exchanger Duty, MMBtu/hr 13.06 11.99
Lean Amine Cooler Duty, MMBtu/hr 12.71 8.83
Acid Gas Condenser Duty, MMBtu/hr 10.54 11.09

Potential areas for improvement in this case would include a reduction in the circulation rate,
an increase in amine concentration, a lower stripper reflux ratio and a reduction in the overall
reboiler duty. Typically, a reduction in circulation rate and heat input to the reboiler are the
obvious areas for improvement. However, some plants have been optimized by increasing
circulation rate to minimize rich acid gas loadings and corrosion associated with acid gas
flashing in the rich amine.

Optimization isn't limited to adjustment of process parameters either. Process optimization

could include installation of an on-line lean amine loading analyzer, reconfiguration or
installation of mechanical and carbon filtration and switching amines, to name a few.

The sequence that should be followed when trying to reduce circulation rate and energy input
into the plant is to first reduce the circulation rate while maintaining the same energy input
into the reboiler. Decreasing the circulation rate first, w illreduce the sensible heat load in the
stripper and result in a higher stripper reflux rate and approximately the same or lower lean
acid gas loadings which will keep the treated gas at current levels. Process parameters to
watch when reducing the circulation rate include rich amine temperature, treated gas
temperature, rich amine loadings and treated gas H2 S and/or C02 composition. Depending on
the amine employed, there are guidelines on maximum rich loadings and rich amine
temperatures as listed in Table 4. Of course the plant should not be allowed to go off
specification and increases in temperature of the treated gas will result in a higher load on
downstream dehydration equipment. After the optimum circulation rate has been determined,
heat to the reboiler can be reduced while
Example Continued

closely monitoring treated H2 S and/or C02 in conjunction with lean amine loadings to make
sure they don't exceed the specification and maximum recommended guidelines as also
outlined in Table 4.

When either the maximum lean loading is exceeded or the treated outlet composition is
bumping the spec, the optimum heat input to the reboiler has been established.

Target values for this example are 264 8pm and 14.96 MMBtu/hr heat input to the reboiler.
These target values were determined by utilizing the following four step process:

1) Ratio current to design gas rates

2) Multiply gas ratio by design circulation to get target lean solvent flow rate
3) Ratio target to design circulation rates
4) Multiply solvent ratio by design reboiler duty to get target reboiler duty

TARGET FINAL OPTIMIZED

Wt% MDEA 50.0 S0.0

Amine Circulation, 8pm 264 264
Stripper Reflux Ratio, mole/mole . 1.20 1.20
Reboiler Duty, MMBtu/hr 14.96 13.83

Listed below is a summary of the baseline data compared to optimized conditions.

BASELINE OPTIMIZED

Inlet Gas Flow, MMSCFD 30.0 30.0

Inlet Gas Pressure, psia 850 850
Inlet Gas Temperature, Deg F 100 100
Inlet H2 S, mole% 7.0 7.0
Inlet C02 , mole% 3.0 3.0
C02 Specification, mole% 2.0% MAX 2.0% MAX
C02 In Treated Gas, mole% 1.13 1.51
H2 S Specification, ppm <4 <4
H2 S In Treated Gas, ppm 0.54 2.90
Wt% MDEA 40.0 50.0
Amine Circulation, 8pm 350 264
Lean H2 S Loading, mole/mole 0.002 0.005
Rich H2 S Loading, mole/mole 0.385 0.409
Lean C02 Loading, mole/mole 0.002 0.005
Rich C02 Loading, mole/mole 0.110 0.098
Lean Amine Temperature, Deg F 110 110
Rich Amine Temperature, Deg F 141 149
Rich Amine Entering Stripper, Deg F 217 226
Example Continued
BASELINE OPTIMIZED

Stripper Overhead Temperature, Deg F 213 206

Stripper Reflux Ratio, mole/mole 2.0 1.2
Stripper Bottoms Temperature, Deg F 245 247
Stripper Bottoms Pressure, psig 10.0 10.0
Inlet Temperature To LA Cooler, Deg F 167 168
Reboiler Duty, MMBtu/hr 20.94 13.83
X-Exchanger Duty, MMBtu/hr 11.99 8.91
Lean Amine Cooler Duty, MMBtu/hr 8.83 6.55
Acid Gas Condenser Duty, MMBtuthr 11.09 6.29

A review of the optimized process parameters compared to the old baseline conditions
shows several immediate savings and benefits:

1) Reduced amine pumping requirements resulting in lower power or steam

consumption depending on the type of pump employed

2) Reduced air and/or water requirements for lean amine cooler and acid gas
condenser

3) Increased C02 slip resulting in higher concentration of H2 S to downstream

sulfur recovery equipment

4) Reboiler energy savings of $74,655/yr based on a 350 day operating year and
$1.25/MMbtu.

When a systematic approach is taken to amine plant optimization, the results are usually
immediate money savers in addition to being sustainable.

SUMMARY

There really isn't any mystery to amine plant troubleshooting and optimization. All that is
required is a fundamental approach with a basic understanding of the amine process.
Hopefully we have presented a systematic method for troubleshooting and optimization of
amine plants, that if properly utilized, will result in fewer plant upsets, quick and correct
responses to changing conditions and long term profitable operation of any amine unit.
REFERENCES

1. Stewart, E.J., Lanning, R.A.; "A Systematic Technical Approach To Reducing Amine
Plant Solvent Losses", Proceedings of the 1991 Gas Conditioning Conference.

2. DuPart, M.S., Bacon, T.R., Edwards, D.J.; "Understanding and Preventing Corrosion
In Alkanolamine Gas Treating Plants", Proceedings of the 1991 Gas Conditioning
Conference.
 TABLE 1

TROUBLESHOOTING GUIDE FOR "FAILURE TO MEET SPECIFICATION"

- Acid gas concentrations in inlet gas have changed

- Feed gas temperatures have changed
>120 Deg F for H2S
<75 Deg F for C02
- Lean amine solution is too hot
Fouled cross exchanger and/or lean amine cooler
Undersized cross exchanger and/or lean amine cooler
High ambient temperature
- Amine concentration too high or too low
Lack of equilibrium driving force (too high)
Inadequate moles of amine for moles of C02 and/or H2S (too low)
- Inadequate lean loading
Poorly stripped solvent
Insufficient stripping steam in stripper
Low/high stripper pressure
Foaming in stripper
Contaminated solvent
Circulation rate below minimum turn down
Loss of trays or plugged packing
Other sulfur species causing high partial
pressure
Leak in lean/rich cross exchanger
- Amine feed tray too low in absorber
Not enough stages for required removal
- Loss of contact trays / plugged packing in absorber
No stages for removal
Poor distribution / lack of contact between gas and amine
- Amine circulation rate too low
Not enough moles of amine for moles of C02 and/or H2S
- Gas pressure has dropped
Driving force for removal reduced
- Contactor operating below minimum turn down
Poor hydraulics / loss of efficiency
- Maximum gas flow exceeded
Jet flooding / poor hydraulics / loss of efficiency
- Degraded solvent (heat stable salt build-up)
Less moles of active amine available for acid gas removal
Oxygen in feed gas
Thermal degradation
Carboxylic acids in feed gas
- Mechanical damage
Collapsed trays / broken packing
Plugged and/or broken distributors
Corrosion
- Contaminated/dirty solvent
Well treating chemicals
FeS
Corrosion products
- Foaming (See Table 2 for a more detailed outline)
 TABLE 2

TROUBLESHOOTING GUIDE FOR "FOAMING"

SYMPTOMS
- Fluctuating absorber or stripper delta P
- Amine carryover from absorber, stripper or flash tank
- Swinging liquid levels in any vessel
- Decrease in H2S removal with increase in C02 removal
- Off specification treated gas
- Positive results from foam test
- Poorly stripped solvent

CAUSES
- Hydrocarbons + organic acids ==> amine soaps
Poor inlet gas separation
Lean amine temperature too low
- Well treating fluids and corrosion inhibitors
Inadequate inlet gas separation
- Oil, inhibitors and welding fluxes
Improperly cleaned equipment
- Suspended solids* (FeS, carbon fines, colloidal iron oxide)
Poor inlet gas separation
Inadequate solution filtration
- Raw cotton filters
Improper selection of filter material
- Make-up water
Corrosion inhibitors from steam condensate system
Bacteria

PREVENTION

MAINTAINING A CLEAN SYSTEM IS THE KEY!!

- Maintain lean amine temperature 10 Deg F above inlet gas temperature to minimize hydrocarbon condensation
-Adequate inlet gas separation to minimize liquid hydrocarbons, iron sulfide/suspended particles and well treating
chemicals from entering the amine system - Proper clean-out of new equipment prior to start-up - Adequate carbon and
mechanical filtration - Foam test with proposed make-up or initial fill water - Proper mechanical filter material
selection - Temporary use of antifoams
Either silicone, polyglycol or high MW alcohols
Antifoam usage in most cases should be considered a temporary treatment while the root cause(s) is
identified and corrected

* Suspended solids do not cause foaming, but rather stabilize the foam
 TABLE 3

TROUBLESHOOTING GUIDE FOR "AMINE LOSSES"

MECHANICAL LOSSES
Both Gas/Liquid & Liquid/Liquid Applications:
- ANY permanent, unwanted or unscheduled physical removal of solvent from the plant.
- Leaks at pipe flange/gasket connections. - Pump seal flushes or leaks.
- Pressure gauge / sample line purges. - Frequent filter changes.
- Unrinsed cartridge filter elements. - Unrinsed carbon bed.
- Amine sump contamination/disposal. - Excessive daily sample volumes.
- Heat exchanger leaks.

ENTRAINMENT LOSSES
Gas/Liquid Applications Only:
- Unwanted or uncontrolled liquid in gas dispersions (mists/sprays) formed.
- Tower diameter too small for gas flow. - Tower pressure below design.
- Trays at or above flooding. - Trays damaged or plugged.
- Amine distributors undersized or plugged. - Damaged or missing mist eliminator pads.
- Damaged knock-out vessels.

- Unwanted or uncontrolled gas in liquid dispersions (foams) formed.

-Refer to Table 2.

Liquid/Liquid Applications Only:

- Unwanted or uncontrolled liquid in liquid dispersions (emulsions) formed.
- Fluid velocity greater than 15 USGPM/ft 2. - Packing material not steel-or ceramic construction.
- Amine distributor orifice velocity > 170 ft/min. - Amine superficial velocity > 60 ft/hr.
- Hydrocarbon superficial velocity > 130 ft/hr. - Damaged tower internals.
- H.C. disperser orifice velocity > 1.25 ft/sec.

SOLUBILITY LOSSES
Liquid/Liquid Applications Only:
- Amine concentrations greater than 40 wt%. - High system temperatures.
- Low system pressures. - MEA > DEA > MDEA.

VAPORIZATION LOSSES
Both Gas/Liquid & Liquid/Liquid Applications:
- High amine concentrations. - High system temperatures.
- Low system pressures. - MEA > DGA > DIPA > MDEA > DEA.

DEGRADATION LOSSES
Both Gas/Liquid & Liquid/Liquid Applications: Chemical
degradation - Reaction with carbon dioxide (MEA & DEA
only). - Reaction with oxygen (all amines). Thermal
decomposition - Skin temperatures greater then 350 Deg F.
Heat Stable Salt Formation - Inlet gas contaminants. - Oxygen
degradation. - Thermal degradation by-products.
 TABLE 4
TROUBLESHOOTING GUIDE FOR "CORROSION"

TYPES OF CORROSION
- General Corrosion
- Uniform material deterioration.
-Galvanic Corrosion
- Dissimilar metallurgy coupled together in the presence of an electrolyte.
-Crevice Corrosion
- Concentration cells are allowed to form in stagnant areas of the system.
-Pitting Corrosion
- Stagnant areas with high halide ion content accelerate this condition.
-Intergranular Corrosion
- Most often found in stainless steels in heat affected zones.
-Selective Leaching Corrosion
- Removal of one element from a metallic alloy.
-Erosion Corrosion
- High flow rates and turbulence can accelerate attack on a metal.
- Aggravated by the presence of solid particles or entrained gas bubbles.
-Stress Corrosion Cracking
- Simultaneous presence of tensile stress and corrosive media.
- Presence of chloride ion can induce this phenomenon.
-Hydrogen Damage Corrosion
- Mechanical damage caused by the presence of, or the interaction of the metal with hydrogen.

SYMPTOMS
- High solution metals (Fe, Cr, Ni, etc.) content. - Vessel failure.
- Wall thinning using ultrasonic monitoring. - High rates on coupons or probes.
- Physical leaks. - Positive solution corrosivity test.

PROCESS CONSIDERATIONS
- Rich acid gas loading too high due to low amine concentrations or under-circulation of amine.
- There is potential for corrosion at total acid gas loadings greater than:
-0.35 moles acid gas/mole MEA. - 0.40 moles acid gas/mole
DEA. - 0.45 moles acid gas/mole MDEA.

- Residual lean amine acid loadings too high due to insufficient stripping.
- Lean side acid gas flashing can occur if lean loadings exceed:
-0.15 moles acid gas/mole MEA. - 0.07 moles acid
gas/mole DEA. - 0.01 moles acid gas/mole MDEA.
- Poor quality make-up water adds contaminants to the amine system which enhance corrosion.
- Water quality to amine plants should not exceed:
-100 ppm for total dissolved solids. - 50
ppm for total hardness as calcium ion. - 2
ppm for chloride ion. - 3 ppm for sodium
ion. - 3 ppm for potassium ion. - 10 ppm
for dissolved iron.

- Presence of heat stable salts will enhance corrosion.

 TABLE 4 (cont'd)

TROUBLESHOOTING GUIDE FOR "CORROSION"

PROCESS CONSIDERATIONS (cont’d)

- Incorrect amine chosen for the intended use.
- Improper metallurgy in all or part of the system.
- Solution flow velocities exceeding 3 ft/sec. in carbon steel and 8 ft/sec. in stainless steel.
- Large step changes, either increases or decreases, in piping internal diameters.
- Short radius elbows.
- Flange gasket material protruding into pipe flow area causing a restriction or turbulence.
- High suction pressure drop across pumps.
- Insufficient available net pump suction head.
- Control valves improperly located.
- Inadequate mechanical and/or carbon filtration.
- Non-stress relieved or insufficiently stress relieved hardware being used.
- Inlet gas knock-out under-designed, allowing contaminants to enter amine solution.
- Suction side leaks and no pad gas on tanks, sumps, etc. thereby allowing oxygen into the system.
- Bulk solution temperatures exceeding 260 Deg F.