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CHEVRON RESEARCH AND TECHNOLOGY COMPANY

Richmond, California
Light Hydrocarbon processing Team

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

JULY 1994

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

;TABLE OF CONTENTS

Page
1.0 INTRODUCTION
1.1 Purpose
1.2 Objective
1.3 Scope

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2.0 AMINE TREATING


2.1 Process Description .
2.2 Operating Parameters
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2.3 Process Control
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2 . 4 Equipment . . . .

3.0 SOLVENT CHARACTERISTICS


3.1 Amines
3.2 Performance
3.3 Solution Quality
3.4 Amine Degradation
3.5 Heat Stable Salts
3.6 Foaming
3.7 Losses
3.8 Makeup Water
3.9 Filtration
3.10 Reclaiming

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. . 1. 1
. . . . . . . . 1. 1
. . . . . . . . 1.2

2. 2
. 2.9
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2.15

2.22

3.1
3.2
3.5
3.7
3.10
3.13
3.14
3.18
3.18

3.21

4.0 CORROSION CONTROL


4.1 Corrosion in Amine Treating Plants. . . . .
. 4.1
4.2 Influence of Design and Operating Variables . . . 4.6
4.3 Use of Alloy Equipment . .
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. . . . . 4.8
4.4 Corrosion Inhibitors.
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4.10
4.5 Corrosion Monitoring
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4.11
5.0 MONITORING PLANT PERFORMANCE
5.1 Performance Goals
5.2 Recommended Practice
5.3 Sampling and Analysis
5.4 Monitoring Trends

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. . .

6.0 ENVIRONMENTAL ISSUES


6.1 Refinery Fuel Gas Sulfur Content . . .
6.2 Disposal of Wastes from Amine units

6.1
6.2

.7.0 ADDING CAPACITY TO AN AMINE UNIT


7.1 Determining the Capacity of an Amine unit . . . . .
7.2 Temporary Operation at Elevated Rich Amine Loadings
7.3 Debottlenecking an Amine Unit . . . . . .
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7.4 Switching from DEA or MEA to MDEA . . . . . . . . .
TABLE OF CONTENTS

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5.1
5.1
5.7
5.7

7.1
7.5
7.6
7.9

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

8.0 PROCESS SIMULATION

8.1
8.2
8.3
8.4

Introduction . . . . . . . . .
How to Create a Simulation of an
TSWEET . . . . .
AMSIM (or HYSIM) . . . . .

8. 1

Existing Amine unit 8.2


. . . . . . . . .8. 3
8. 4

9.0 TROUBLESHOOTING
10.0

HYDROCARBON/PARTICULATE REMOVAL BEST PRACTICE

TABLE OF CONTENTS

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

1.0

INTRODUCTION

1.1

PUrpose

The purpose of the "Amine Treating Best operating Practices


Resource Guide" is to assist in the achievement of effective,
reliable, economical, and environmentally sound operation of
amine units.
The guide addresses the removal of H2S and C02 (or "acid gases")
from either gas or LPG streams, and is applicable to amine units
in refineries as well as those in upstream facilities. In
general, the guide emphasizes performance improvement and
troubleshooting over design, and is meant to complement best
practice guides developed by the refineries.
.
The guide does not cover processes for acid gas removal using
physical solvents, hybrid solvents, caustic or sorbents. Removal
of trace amounts of sulfur compounds including H2S, COS,
mercaptan and CS2 are covered in a separate guide.
1.2

Objective

The objective of the guide is to help find the best operating


practices for a particular amine unit. The discussion covers the
operating principles of amine units, common problems that occur,
techniques used to recover from operating problems and strategies
to avoid problems in the future.
The input to the guide comes from a variety of Chevron and
industry experience. Because of the wide range of conditions
upon which that experience is based, it is not unusual to find
contradictions among the various practices that have been
prescribed to operate or fix amine units. There are few absolute
"best practices" that can be applied rigorously to all amine
plants. strict adherence to a standard list of parameters is not
necessarily the best practice. General rules can sometimes be
broken without serious consequence. Each amine unit has its own
tolerance for abnormal conditions which can only be gauged
accurately through consistent monitoring and attention.
On the other hand there are some basic principles that well run
amine units follow. What is presented here is a guide (or
process) that c~n be used to evaluate the performance of amine
units and set operating parameters accordingly. A major intent
of the guide is to help determine what steps should be taken to
directionally improve performance.

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

The key to best operating practice for amine units is to avoid


conditions which "stress" the unit; and when problems do develop
it is best in the long run to treat the source of the problem
rather than the symptom.
1.3

Scope

The following are included within the scope of the guide:


The process flow, parameters and equipment of amine units,
Characteristics of amine solvents,
Typical operating problems (such as foaming and corrosion)
and how to minimize them,
The use and interpretation of analytical and operating
data for day-to-day monitoring, troubleshooting and
quality control,
Environmental concerns,
Use of simulators to evaluate and/or tune the unit,
Considerations for increasing plant capacity.

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

2.0

AMINE TREATING

Amine treating (or sweetening) is used in a wide variety of


applications to remove H2S and C02 from gases and light
hydrocarbon liquids. The purpose of the process is to reduce the
concentration of the acid gas contaminants sufficiently to meet
product sales, flue gas emissions or other process requirements.
The process has changed very little over the many years it has
been in use. Over the past decade, however, the generic
alkanolamines such as MEA, DGA, DEA, and DIPA have been joined by
MDEA and proprietary solvents in a move toward increased energy
efficiency, reduced corrosion rates and enhanced performance.
Gas and liquid feed streams are treated fundamentally the same,
except for some differences in the absorber design and some
specific operating considerations which will be identified later.
For simplicity of presentation, the process will be described in
terms of gas treating which is more common.
The majority of operating problems in amine plants have to do
with the fact that the solvent undergoes continuous thermal
cycling in a closed loop, and that feed gas contaminants and
degradation products formed during operation can build up in the
solvent and lead to foaming, liquid carryover, off-spec product,
corrosion and erosion. These conditions can be aggravated by
operating the unit outside the recommended ranges of temperature,
amine loading, amine concentration, feed composition and fluid
velocities. Inherent design details and materials selection also
play a role here. Understanding the process principles is the
first step in achieving best operating practices for amine units.

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

2.1

Process Description

The process is based on the simultaneous diffusion of acid gases


into and out of the aqueous solvent phase and the reversible
chemical reactions that take place between the amine and acid gas
components. These reactions and other characteristics of the
different amines are discussed in section 3.0.
The choice of amine has an influence on plant economics (e.g.
capital, solvent and energy costs) and the ability to achieve the
required treated gas specifications. The process flow is
conceptually the same regardless of the type of amine used.
The two main processing steps in amine units are:
i) Chemical Absorption. Feed gas (or "sour" gas) is
contacted with "lean" amine in an absorber column to remove
the acid gases. The treated gas (or "sweet" gas) leaves the
top of the absorber. The objective may be:
"simul taneous removal II of H2S and C02 to low levels
(i.e. 4ppmv H2S and 100 ppmv C02 for gas plants or
less than 160 ppmv H2S with no concern for C02 removal
for refineries),

"bulk removal" of C02 (ie. from, 4 mol% to 2 mol% to


meet sales gas specification) or

"selective removal" of H2S to low levels while


"slipping" C02 (i.e. reduce H2S to 4 ppmv and C02 from,
say, 4 mol% to 2 mol% for gas plants or less than 160
ppmv H2S with minimum C02 absorption for refineries).

ii) Solvent Regeneration. The "rich" amine containing the


acid gases is regenerated by stripping them out in a
distillation column. The acid gases are recovered from the
regenerator overhead and typically sent to a sulfur recovery
unit (SRU) or incinerator. If only C02 is being removed the
regenerator gas is vented. The objective is to:
reduce the residual "loading" of the lean amine so that
the acid gas equilibrium vapor composition is equal to
or less than the specified composition of H2S and C02
in the,treated gas.

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Typical Amine Process Flow


A typical flow sheet is shown in Figure 2.1
Absorber Feed streams
Depending on the condition of the sour gas, it may be necessary
to prepare it for the absorber by first passing it through a
knockout drum, centrifugal separator and/or filter separator to
remove liquid carryover, condensed liquids and particulates which
can cause foaming in the absorber and regenerator. In refineries
a water wash column may preceed the absorber to remove organic
acids.
The "clean" sour gas passes into the lower section of the
absorber, up the column through contacting trays or packing and
out the top (water saturated). Pressurized lean amine solution
enters at the top of the absorber at 100-140 deg F and flows down
contacting the gas counter-currently.
The lean amine should be 10-15 deg F hotter than the feed gas to
ensure that no hydrocarbons are condensed and that any mist
carried over from the knockout drum will be vaporized. In very
sour streams .this temperature difference may have to be increased
to account for the dew point elevation caused by removal of the
acid gas. The upper limit on lean amine temperature for
effective absorption is 140 deg F while the upper limit of feed
gas temperature is 120 deg F.
The amine absorbs the acid gases and leaves the bottom of the
absorber. Small amounts of hydrocarbon gases are dissolved into
the amine, as well. Refinery gases often contain ammonia. Some
ammonia will be absorbed in the amine.
Absorber Outlets
The streams leaving the absorber are hotter than the feed streams
due to the exothermic heats of reaction from absorbing the acid
gases. Treated gas from the overhead of the absorber passes
through a knockout drum and/or water wash to remove and recover
entrained amine.
Rich amine from the absorber bottoms is let down through the
absorber level control valve to a flash drum.
Rich Amine
The flash drum provides residence time to separate amine from
liquid hydrocarbon phase (resulting from entrainment or
condensation in the absorber) and releases light hydrocarbon
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vapors and small quantities of acid gases from the rich amine.
In some units the flash gas may pass through a small amine
absorber mounted on top of the flash drum so that the gas may be
used as fuel. Evolution of light hydrocarbons is important prior
to amine regeneration to avoid foaming and sending excessive
hydrocarbons along with acid gases to the SRU. Some plants are
designed with rich amine filtration at the flash drum liquid
outlet to remove particulates carried into the system with the
feed gas. However, filtration is typically carried out on the
lean amine side where exposure to H2S is minimized. Filtration
can be done at either location. Refer to sections 2.4 and 3.9
for further discussion.
Next, the rich amine flows through the tube side of the lean/rich
. exchanger to recover heat from the regenerator bottoms stream.
The hot rich temperature is dependent on the physical
characteristics of the exchanger, solvent properties and solvent
flow rate. It is possible for a clean or new exchanger to
develop hot rich temperatures higher than design. The "hot rich"
amine within the exchanger and in the exchanger outlet piping is
conducive to corrosion and erosion particularly when the rich
loading is high and the hot rich temperature exceeds about 215
deg F. At such conditions H2S and C02 can break out of solution
into the vapor phase in amounts sufficient to cause severe
corrosion problems.
In units where the flash drum level control valve is located at
the L/R exchanger outlet and there is no rich amine pump, the
flash drum pressure influences the amount of vaporization that
occurs within the exchanger. Some natural gas plants are
designed with a "high pressure" operating mode (150-200 psig) for
the flash drum which has the effect of limiting the evolution of
acid gas vapor in the lean/rich exchanger, thus minimizing
erosion and corrosion within the exchanger, outlet piping and
fittings. The hot amine then flashes across the flash drum level
control valve and flows a short distance to the regenerator
inlet. However, as a general rule the flash drum is typically
set at the lowest practical operating pressure to minimize
hydrocarbon content of the amine going into the regenerator and
on to the SRU.
Amine Regeneration
The rich amine from the flash drum is preheated by passing
through the lean/rich exchanger and fed to the top of the
regenerator. The regenerator typically operates at low pressure
(10-20 psig) and elevated bottoms temperature (230-260 deg F),
conditions which favor the desorption of the acid gases. The
amine flows down through the trays as the acid gases are stripped
out by steam passing up the column. Steam is generated from the
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

water in the amine solution on the shell side of the reboiler.


It is desirable to operate the reboiler at as low a temperature
as possible while maintaining the necessary heat flux (6-8
Mbtu/hr/sqft). 50 psig steam, typically 1 pound of steam per
gallon of circulating solvent, is the usual heat medium used in
amine reboilers. Hot oil loops and direct fired heaters can also
be used. Excessive reboiler tube skin temperatures (above 320350 deg F) cause increased rates of thermal degradation of the
amine and should be avoided.
units using primary amines like MEA and DGA are often designed
with a reclaimer which takes a sidestream from the regenerator
bottoms equal to 1-3% of the amine circulation rate. After
adding caustic to convert amine salts to sodium salts the
reclaimer boils off an amine/water mixture in a batch operation
leaving behind degradation products, suspended solids, acids and
iron compounds. Reclaimers are essential in DGA plants to
reverse degradation caused by cos. Reclaimers are not usually
provided for DEA and MDEA units because it is assumed degradation
is less severe than for primary amines, and because they have
lower volatilities which would mean operation of the reclaimer
under vacuum requiring greater expense and operator attention.
other methods of reclaiming are discussed in section 3.10.
Regenerator overhead vapor consists of acid gases, ammonia (in
refineries) and water vapor. Most of the water is condensed in
the regenerator overhead condenser and collected in the reflux
drum. Some ammonia will form ammonium biSUlfide, soluble in the
water. The sour water from the reflux drum is returned to the
top of the regenerator and the acid gases are sent to the SRU,
incinerator or vent.
Ammonia Scrubber
In refineries it is common to water wash the offgas in a packed
scrubber column to remove ammonia before routing the acid gas to
the SRU. This processing step minimizes the precipitation of
ammonium bisulfide in the line to the SRU.
Makeup water
A portion of the sour water may be purged from the reflux drum to
provide an outlet for contaminants and to control ammonium
bisulfide concentration. The purge rate should be adjusted
according to regular test results for ammonium bisulfide content
of the sour water. Makeup water or steam.is added to the solvent
inventory as required to maintain the water balance (see section
3.8).

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Lean Amine
Lean amine from the regenerator bottom is cooled in the lean/rich
exchanger and pumped through an air or water cooled exchanger.
Then,the amine passes through a particulate filter (preferably
full flow) to remove iron sulfide scale, iron carbonate
precipitate (from corrosion), insoluble degradation products, and
other particles. In plants where full flow filtration is not
available and the system is relatively clean, filtration of a 25%
slipstream may be sufficient. A 5 or 10 micron absolute filter
is typically used. Backwash filtering systems may require
additional tankage. Filters may be located on the rich or lean
amine, or both.
A 10-20% slipstream of cooled lean amine may be treated by
activated carbon to adsorb hydrocarbons which would otherwise
build up in the amine solution and cause foaming (see section
3.9). The carbon bed may be followed by a second particulate
filter to catch entrained carbon fines.
Amine Storage/Surge
Some units have a storage/surge tank which provides volume to
accommodate swings in amine inventory and liquid levels.
Otherwise, surge capacity is provided in the bottom section of
the absorber, regenerator and/or flash drum. Concentrated amine
for make-up may be stored in a tank. Both tanks are blanketed
with fuel gas or nitrogen. Air should be excluded from the
storage tanks to prevent oxygen degradation of the amine which
can cause increased levels of precursors to corrosive compounds.
Finally, the lean amine is pumped back to the top of the
absorber
. Chemical Injection
Provisions are usually made to add antifoam (see section 3.6) and
sometimes corrosion inhibitors (see section 4.4) and caustic (see
section 3.5) to the lean amine by injection pump or shot pot.
General
Skim nozzles are often provided in the absorber, regenerator,
flash drum and reflux drum to skim any hydrocarbon layer that may
accumulate. A more effective means of hydrocarbon removal in the
flash drum is by means of three-phase separation with a weir and
an overflow sump at one end for removal of the hydrocarbon phase.
split Flow
An

alternative design shown in Figure 2.2 circulates a semi-lean

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

amine in addition to the usual lean amine to minimize the


operating cost of amine regeneration. The semi-lean amine is
withdrawn from the middle of the regenerator and fed to the
middle of the absorber where acid gas concentration is high. The
lean amine from the bottom of the regenerator is reserved for
contacting the gas in the upper part of the absorber. Less lean
amine is needed to achieve the same treated gas specifications,
thus less energy is expended in the reboiler. However, the semilean stream requires separate pumps and exchangers.
Selective B2S Removal
Significant energy savings can be made by selectively removing
H2S from a feed gas which also contains C02. If C02 removal is
not required then MDEA or proprietary solvents (such as UCARSOL
HS-10l or Flexsorb SE) are available which allow 70% or more of
the C02 to "slip" through the absorber.
Also, slipping C02 may be desirable in some cases from the
standpoint that C02 acts as a diluent and takes up space in
Sulfur Recovery units.
When C02 removal is minimized it is possible to realize benefits
in terms of increased throughput capacity, lower amine
circulation rates, improved compliance with environmental
regulations and lower regeneration energy. Proprietary selective
solvents are more expensive than the primary and secondary
amines, however.
The process takes advantage of the slower reaction rate of C02
vs. H2S with tertiary amines. The absorber may be designed with
fewer stages (12-15) than normal (20-25) or with multiple lean
amine feed points to adjust the solvent residence time to achieve
the desired amount of slip. Too few stages in the absorber could
risk H2S breakthrough.
Bulk C02 Removal
Bulk C02 removal is often used to meet pipeline sales gas
specifications when complete C02 removal is not required. For
example, MDEA can reduce C02 from 4% to 2% by slipping half the
C02 through the absorber. Bulk C02 removal requires similar
considerations as described above for selective H2S removal.
Alternatively, in the above example, the same effect can be
achieved by feeding half the gas to a DEA absorber and
recombining with the untreated half.

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Liquid Treating

Light hydrocarbon fractions or LPG can be sweetened in similar


fashion to gas. In the absorber, LPG becomes the dispersed phase
traveling up through the continuous amine phase with interface
control at the top of the absorber. The majority of
liquid/liquid treaters employ packed absorbers although trayed
absorbers are also used. Because of the small density difference
between phases and solubility of amine in LPG, managing amine
losses is a major operating concern. Liquid treaters tend to be
the largest source of solvent losses in refineries. Due to the
small density difference between the phases, tower design errors
and poor operating conditions have a tremendous impact on losses.
In practice, solvent entrainment in the hydrocarbon phase is far
more significant than amine solubility.

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2.2

Operatinq Parameters

The objectives of an amine unit are to produce a treated gas that


meets the required residual acid gas specifications and to
provide a clean acid gas from the regenerator overhead. Ideally,
these objectives are to be achieved with high reliability and
optimal operating costs. To this end there are various key
parameters that have to be considered.
Key operating Parameters
The key operating parameters to consider in an amine unit are:
Feed Gas:

Flow Rate
Inlet Temperature (80-120 deg F)
Inlet Pressure (100-1000+ psig)
Hydrocarbon Dew Point
H2S, C02 Concentration or Partial
Pressures (1-50+ psia)

Acid Gas:

Outlet Pressure (10-20 psig)


Outlet Temperature (100-130 deg F)

Amine:

Lean Temperature (100-140 deg F)


Circulation Rate
Amine Concentration (wt %)
Amine degradation

Regenerator:

Reboiler steam Rate (0.9-1.2 lb stm/gal)


Reflux Ratio (1.5-4.0 moles water
returned to regenerator per mole acid
gas from reflux drum)

Flash Drum:

Pressure (2-150 psig)

~~_/

Contaminant Removal:
Entrained or dissolved hydrocarbon
Particulates
Trace sulfur species
Organic acids
Parameters Influencing Acid Gas Concentration of the Treated Gas
At a particular. set of feed gas and circulation rates, the acid
gas concentration of the treated gas leaving the absorber is most
directly impacted by three process variables:
Lean amine temperature at top tray
Lean amine loading
Amine circulation rate
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Lean amine temperature is constrained by the available cooling


medium temperature and a differential above the inlet gas
temperature. The lean loading is a function of reboiler duty
which can vary within limits of the equipment. The lean amine
circulation rate may be adjustable to some degree and determines
the rich amine loading. As an example, the following table shows
the sensitivity of the treated gas to lean loading and lean
temperature using a basis of 30 wt % DEA assumed to be at
equilibrium with the treated gas at the top of the absorber:
30 wt% DEA in Equilibrium with B2S
at Typical Absorber Overhead Conditions
Pressure
(Psia)

PPMv B2S at Temp.


Lean Loadinq
(Mols B2s/mol Amine) 100 eD F 125 eD F

500
250
100

.01
.01
.01

0.9
1.8
4.5

1.5
3.0
7.5

500
250
100

.02
.02
.02

3.3
6.6
16.5

6.6
13.2
33.0

The table above shows that a 25 deg F increase in lean amine


temperature on the top tray increases the partial pressure (and,
therefore, concentration) of H2S in the treated gas by 50-100%.
The effects of total pressure and lean loading are also shown.
Simulator predictions of equilibrium concentrations in the low
ppm range often differ from the actual values so they should be
used with caution.
Equilibrium Curves
Figures 2.3,4 & 5 show examples of equilibrium curves for MEA,
DEA and MDEA. These curves represent partial pressure of H2S or
C02 plotted against amine loading. They provide a graphical
means of estimating the upper limits of capability of an amine
unit. It would be necessary to plot a family of curves to look
at partial pressures when both H2S and C02 are present. These
curves were generated using the AMSIM program.

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Approach to Equilibrium
Amine absorbers in HzS removal service tend to have more than
enough stages so that virtually 100% "approach to equilibrium"
between the vapor and liquid is normally achieved in the upper
section. For HzS removal it is usually desirable to operate in
the "lean end pinch" mode such that the operating curve and
equilibrium curve converge somewhere in the upper third of the
absorber. This means that the partial pressure of HzS in the
treated gas (and thus, the "parts per million HzS") very nearly
approaches the equilibrium partial pressure of HzS over the lean
amine; the HzS equilibrium partial pressure is determined by the
degree of stripping in the regenerator. A thorough discussion of
this topic is available in References 2.1 and 2.2.
C02 is less likely to reach complete equilibrium with the lean
amine due to slower reaction kinetics depending on the specific
amine. (Reactivity decreases going from the primary amines, MEA
and DGA, to tertiary amine, MDEA). Additional stages and high
weirs (4 inches) may be employed to maximize C02 removal. Fewer
stages and lower weirs may be employed to minimize C02 removal
when using MDEA or proprietary solvents designed to slip C02
intentionally.

As implied above, the residual acid gas content of the treated


gas can be expressed in terms of "approach to equilibrium" or
ATE. It is useful to be familiar with the ATE concept when
evaluating amine unit capacity and performance. ATE at top tray
conditions is:
(measured lean loading in solvent to the absorber> x 100%
(lean loading in equilibrium with treated gas)
The equilibrium loading can be obtained from a simulator program
or from the solvent vendor. An unusually low ATE at the top of
the absorber indicates H2S breakthrough or C02 slip due to
insufficient acid gas pickup capacity in the lower section of the
column. ATE at bottom tray conditions is:
(measured rich loading in solvent from the absorber> x 100%
(rich loading in equilibrium with feed gas)
Most of the mass transfer and chemical reaction takes place in
the lower part Of the absorber. Typically, an absorber is
designed for 70% or less ATE (not 100%) at the bottom for the
following. reasons:
to ensure adequate driving force for mass transfer and kinetics
to recover more of the heat of reaction as sensible heat into
the rich amine and less into the treated gas
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to allow for increases in temperature or acid gas content of


feed and prevent acid gas breakthrough or "leakage" overhead
to limit absorber temperature rise due to heat of reaction (due
to concerns for corrosion)
to limit extent of acid gas flashing in the hot rich amine from
the lean/rich exchanger
to minimize corrosion associated with high rich loading
Absorber Temperature Profile
The absorber temperature profile provides useful information on
performance. Typically the profile has a "bulge" in the lower
portion of the column where most of the exothermic chemical
reaction takes place. The temperature in the top half and in the
treated gas out the top should have about the same temperature as
the lean amine. The temperature should increase down through the
bottom half, dropping somewhat on the bottom tray or two as the
incoming feed gas cools the amine. The rich amine out the bottom
should be significantly hotter than the lean into the column.
Thus, the heat should go with the rich amine to the regenerator.
'!'he degree of temperature rise depends on the acid gas content of
the gas being treated.
Amine Loading,
Lean and rich loadings are commonly determined by laboratory
analysis and reported as moles of H2S (and/or C02) per mole of
amine. Rich amine samples are quite likely to be in error, on
the low side, due to vapor losses during sampling. A simple
material balance around an absorber designed for total acid gas
removal can be made to check the rich loading:
Rich Loading
Moles Acid Gas
Moles Amine

=
=

(Acid Gas Pickup from Feed Gas)+(Lean Loading)


(MMSCFD) (Mol% AG in Feed) (Amine Mol wt) (1.832)
(Amine Rate, GPM) (wt% Amine) (Solvent, lb/gal)
+ (Lean Loading)

Note:

"Mol% AG in Feed" includes both C02 and H2S.


Typical
Amine
Amine
Solvent
Solvent
M,ol wt
wt%
lb/gal
@ 120 F

MEA

DEA
DGA
MDEA
AMINE TREATING

61.08
105.14
105.14
119.17

20
30
50
50

8.31
8.53
8.59
8.59

2.12

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Reboiler Heat

Reboiler heat duty (supplied by steam or other heating media)


usually represents the largest operating cost of an amine plant.
If lean loading is much less than required to achieve cleanup
then energy is being wasted. However, some margin of excess duty
is desirable in the event of a change in process conditions.
Also, there is another reason to keep lean loadings low and that
is to avoid lean side acid gas flashing or cavitation at the
suction of the amine circulation pump. Lean loadings should not
exceed the following values:
Amine
MEA
DEA
MDEA

moles of acid gas/


mole of amine
0.15
0.07
0.015

The reboiler provides energy in three parts: sensible heat to


bring the amine up to boiling, latent heat to boil up some
stripping steam and chemical heat to reverse the acid gas/amine
reaction. The heat of reaction is variable depending on the
amine and combination of H2S and C02. Approximate values are
listed below:
Heat of Reaction (Btu/lb of H2S or C02)
H2S
C02

MEA
DEA
DGA
MDEA

550
511
674
522

825
653
850
600

Typically, the reboiler operates with about one pound of steam


per gallon of circulating solvent, but can range as high as two
pounds per gallon. The most important indication of reboiler
performance is the lean loading from the regenerator bottoms.
Reflux Rate

The amount of reflux returned to the regenerator is dependent on


the amount of steam raised in the reboiler. The amount of steam
. raised for stripping depends on the solution purity needed to
meet the treated gas specification, the ratio .of H2S:C02, the
amine and. the regenerator design. Reflux ratios range from less
than 1:1 to 4:1 (moles of water returned to the regenerator per
mole of acid gas leaving the reflux drum). The reflux ratio will
be at the high end of the scale for MEA units and middle to low
end for DEA and MDEA, respectively. This has been explained by
AMINE TREATING

2.13

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

the observation that MDEA is less basic and more easily stripped
to satisfactory levels than theprimary and secondary amines.
For H2S/C02 systems the C02 which evolves actually assists H2S
stripping and may reduce the stripping steam requirement,
accordingly.
Some of the water from the reflux drum may be purged, but most of
it is returned to the regenerator to maintain the water content
of the amine. Makeup water is added to replace the losses going
out with the treated gas and acid gas.
Monitoring of the reflux rate is an important part of managing
the energy input to the unit and ensuring that lean loading and
treated gas specifications are on target. The reflux rate is a
measure of reboiler duty, and may be monitored with this in mind.
Overhead temperature is another indication of the stripping steam
rate and reflux ratio, and is considered a convenient means of
monitoring the reflux rate. An amine plant simulator can be used
to determine the overhead temperature for a given reflux ratio
and column pressure.

AMINE TREATING

2.14

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

2.3

Process Control

Process control techniques can be used to maX1m1ze plant


stability and minimize energy usage and other operating costs.
The effectiveness of process control in amine plants depends on
the degree of automation, operator involvement and timely use of
laboratory results.
While variations will be dictated by the original
design/operating philosophy, process parameters, local
regulations and preferences, the process control objectives are
similar from one amine plant to another. Amine plants are
controlled by a combination of manual and continuous automatic
control devices as well as a number of intermittent controls
which can be automated or operator initiated.
Control set points may need to be readjusted from time to time in
response to changes, whether abrupt or gradual, such as: feed
gas rate and composition (especially acid gas components), amine
strength (including heat stable salts content), amine
contamination, heat transfer surface fouling and ambient
temperature.
The chart which follows is a guide to typical process control
strategies used in amine plants.

AMINE TREATING

2.15

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

AMINE UNIT PROCESS CONTROL


STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

1. ABSORBER

FLO\J

PRESSURE

Absorber LCV should


hold 4-10 minutes
surge volune.
Operator skims
hydrocarbon layer
when needed.
Submerged gas feed
may be permissible
to increase contact
time in absorber if
needed for CO2
absorption.

Maintained by
overhead
back pressure CV; or
floats on downstream
pressure.
Hold maxinun
backpressure on
absorber for lowest
residual acid gas in
overhead.
Higher than normal
pressure drop across
the absorber
indicates foaming or
flooding.

2. FEED (Sour) GAS

Controlled by
upstream process, or
absorber inlet
exchanger.

LEVEL

Usually not flow


controlled unless
there are multiple
absorbers requiring
split flow.

Keep 10-15 deg F


cooler than lean
. amine.
3. OVERHEAD (Sweet)
GAS

4. LEAN AMINE
(Absorber Feed)

Regulated by
absorber overhead
gas PCV; or floats
On downstream
system.
Controlled by
cool ing mediun flow
to lean amine cooler
or air coo l er bypass
TCV.

Controlled by FCV on
discharge side of
amine circulation
~.

Excessive flow
wastes energy.
Insufficient flow
risks high rich
loading, H2S
breakthrough and
corrosion_

Keep 10-15 deg F


warmer than absorber
feed gas. If lean
amine is hotter than
about 120 deg F:
residual acid gas in
overhead may exceed
spec.

Adjust flow
according to rich
loading target
value.

If too cold: liquid


HC may form, CO2
absorption rate
drops and ami ne
viscosity increases.
5. RICH AMINE
(Absorber Bottoms)

AMINE TREATING

Absorber LCV
regulates the
bottoms flow.

2.16

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

6. FLASH DRUM

PRESSURE

FLOW

Flash Drun LCV


should hold 10-15
minutes of surge
volume. Operator
should skim
hydrocarbon layer
when needed_ Tune
the LCV to supply
steady flow to the
regenerator in
preference to a
fixed level in the
Flash Drun.

Controlled by PCV on
the flash gas from
the flash drun.
Set low enough to
flash off most of
the dissolved HC.
If less than 45-65
psig, head will be
inadequate to feed
regenerator without
a~.

Set pressure high


enough to minimize
acid gas breakout in
the L/R exchanger
causing erosion
and/or corrosion.
(Applies to plants
with the flash drun
LCV located at the
L/R exchanger
outlet. )

If the Flash Drun


doubles as the
primary surge
vessel for the
closed loop system,
then the liquid
outlet flow rate
(not level) is
controlled. Low
level indicator or
alarm indicates
when solvent makeup
is needed.

May require fuel gas


to pressurize the
Drun when flash gas
is insufficient.

7. RICH AMINE (L/R


EXCHANGER
OUTLET)

Rich outlet
(See Flash Drun)
temperature is
dependent on the L/R
surface area,
surface foul ing and
circulation rate.

LEVEL

Regulated by Flash
Drun LCV; or by
direct flow control
if Flash Drun serves
as the primary surge
vessel.

A clean or new
exchanger can
transfer excessive
heat to the rich
stream causing acid
gas vaporiZation in
the hot rich outlet
which occurs above
about 215 deg F. In
such cases Flash
Drun pressure shouLd
be increased to help
minimize
vaporization

AMINE TREATING

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JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

8. REGENERATOR

PRESSURE

Regenerator LCV
regulates the
bottoms f low and
should provide 4-10
minutes surge time.

Controlled by acid
gas backpressure CV
on Reflux DrLIII.

This level may


effect the flow
hydraulics in the
return leg from
kettle reboiler,
and NPSH of the
amine circulation

Regenerator pressure
determines the
boiling point of the
solution in the
reboiler. Set
pressure as low as
possible and still
get acid gas to the
SRU. Avoid pressure
so high as to cause
thermal degradation
of the amine.
9. LEAN AMINE
(Regenerator
Bottoms)

Regenerator bottoms
temperature is the
boiling point of the
amine solution which
is dependent on
amine concentration
" and regenerator
pressure; it ~
be controlled In:
adjusting the steam
to the reboiler.

10. ACID GAS

Controlled by the
Reflux Condenser
control system.
Steady temperature
control keeps water
content of acid gas
constant, and helps
stabilize SRU
operation.

11. REFLUX DRUM

pLIIIP.

Regenerator LCV
regulates the
bottoms flow; does
not apply when
regenerator bottom
is use for surge.

Controlled by acid
gas PCV on Reflux
DrLIII.

Ref lux DrLIII LCV


should hold 6-10
minutes of surge
volume.

12. REFLUX (to


Regenerator)

Regulated by Reflux
DrLIII LCV on
discharge side of
Ref lux PLIIIP

13. PURGE (frOm


Reflux DrLIII)

Controlled manually
or by FCV"to purge
contaminants from
the system.

AMINE TREATING

LEVEL

FLOW

2.18

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

PRESSURE

14. MAKEUP WATER


(or STEAM)

FLOW

LEVEL

Controlled manually
or by FCV to
continuously add
fresh makeup water
to the system to
replace purge and
normal losses.
Makeup rate is based
on analysis of amine
strength.

15. MAKEUP AMINE

16. REBOILER

Operator
periodically adds
fresh makeup amine
solution to the
system based on
monitoring of system
inventory.
Reboiler temperature
is dependent on
amine concentration
and regenerator
pressure, and !nne!

Circulation and
boilup rates are
dependent on the
rate of heat input,
hydraul ics and type
of reboiler.

be inde~ndent l~

. manil2!:!lated.
17. REBOILER STEAM

Should not exceed


260 deg F (bulk) or
350 deg F (skin).

Steam supply system. Controlled by FCV on


steam line to
Steam pressure
reboi ler. Adjust
should not exceed 50 according to lean
psig to avoid amine loading target
degradation.
value.
LCV on condensate
pot controls
condensate return.
Operator should
periodically vent
noncondensibles from
the pot if needed.

18. SURGE TANK

AMINE TREATING

Heating coils, if
required.

Slight positive
pressure controlled
by fuel gas blanket
system. Inert head
space is needed to
avoid degradation of
ami ne by exposure to
oxygen.

2.19

Level gauge and


alarms indicate
when inventory is
too low or too
high.
Leave room in surge
tank to hold total
amine inventory in
the event of a
shutdown.

JULY

1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

FLO\J

PRESSURE

19. CARBON BED

LEVEL

Typically regulated
by a manua II y
controlled valve.
Abnormal pressure
differential across
the bed indicates a
bed that has been
in.,roperly installed
or is fouled; it
should be replaced.
Changeout the carbon
bed when lab

analysis shows no
in.,rovement in color
or foaming tendency
in vs. out of the
bed meaning that the
bed is no longer
removing
hydrocarbon.
20. FILTER

Typically regulated
a manus II y
adjusted valve.
by

The operator should


backwash (or change
out cartridge
fil ters) at the
point where the
pressure drop
reaches the
reconmended maxinun
and the mininun
slipstream flow rate
.can no longer be
maintained.
21. FILTER BACKWASH
(for lM"Iits with
backwash-type
fil ters)

Hot water or steam


depending on fi l ter
type.

Automatic
backwashing system
is activated by high
pressure drop across
filter elements.
Cycle time varies
depending on IIIIIOU'It
of particulates or
wax.

22. RECLAIMER
(for MEA or
DGA, only)

AMINE TREATING

Batch operation.

2.20

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

STREAM OR
EQUIPMENT
NAME

CONTROLLED VARIABLE
TEMPERATURE

PRESSURE

23. CHEMICAL
INJECTION
(caustic,
anti foam,
corrosion
inhibitor)

AMINE TREATING

FLO\I

LEVEL

Regulated by
injection pump or
shot pot.

2.21

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

2.4

Equipment

There is no equipment used in amine units that is not used widely


in other refining and gas processing facilities. Amine units
consist of columns, heat exchangers, separator vessels, pumps,
and filters.
Absorber
Absorbers are trayed or packed columns in which rising gas
contacts descending amine. Typical columns have either 20-25
trays or 30-40 feet of packing. Absorbers in hydroprocessor
hydrogen recycle loops typically use only 20' of packing due to
the high driving force for HS absorption and the amount of H2S
that can be left in the swee~ gas (100 ppmv or more). Absorbers
in hydrogen plants frequently have an additional 2-4 trays above
the amine feed tray where water contacts the sweetened gas and
removes any vaporized or entrained amine. This is necessary to
protect the methanator, since amines are methanator catalyst
poisons. The water is withdrawn from the absorber at the tray
above the amine feed tray.
Amine absorber trays often require unusually large downcomer
areas. Amine absorbers are frequently designed for higher than
normal liquid loadings, and amine solutions have a much higher
foaming tendency than liquid hydrocarbons exhibit. The
combination of these two factors make large downcomers common in
amine trays. Many amine absorbers use two-pass or four-pass
trays. In absorbers using MDEA or formulated solvents, the weirs
may be higher than normal in order to provide greater liquid hold
up and thus more time for reaction between CO2 and the amine.
Weirs can be 4" or higher in these applications.
Packed absorbers are designed for a low pressure drop, typically
0.25" of water per foot of packing, due to the high foaming
tendency of amine solutions. Packed sections are usually no more
than 15': this reduces the risk of poor liquid distribution. In
hydroprocessor hydrogen recycle absorbers, typically only one
packed section with one liquid distributor is used. This may
lead to liquid distribution problems and loss of efficiency in
absorbers with packed sections greater than 20'.
The surge volume at the bottom of the absorber should be kept as
small as possible, since surge volume can be provided less
expensively in lower pressure vessels. Four minutes of
circulation volume is a minimum value.
Absorbers may be equipped with mist elimination pads to recover
entrained amine from the treated gas. These pads should be made
from metal rather than plastic. Metal pads will have higher
AMINE TREATING

2.22

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

removal efficiencies, since amine solutions will wet metal


surfaces better than plastic surfaces. Mist elimination pads
will not prevent carryover of amine solution if a foaming upset
occurs in the absorber. In order to capture this amine, a
treated gas knockout drum downstream of the absorber is required.
If a treated gas knockout drum is used, it is not necessary to
use a mist elimination pad in the absorber.
Flash Drum
The flash drum is a separator vessel in which absorbed and
entrained hydrocarbons are disengaged from the rich amine. It is
almost always a horizontal separator. Flash drums typically
operate at pressures between 2 and 150 psig. The flash gas,
. depending on the facility and the concentration of H2S, may be
sent to the fuel gas system, a vapor recovery unit, or a sulfur
recovery unit. For amine units operating at low flash drum
pressures a rich amine pump may be required to overcome
frictional losses and static head in the line to the stripper.
A liquid hydrocarbon phase is frequently produced in the flash
drum. If this phase is not recovered as a separate liquid
stream, much of it will end up in the acid gas from the stripper
reflux drum . This might cause problems in a Claus plant. In
order to remove these liquid hydrocarbons, most flash drums are
designed as three phase separator vessels.
The liquid residence time in the flash drum is determined by the
time required to separate the liquid hydrocarbons from the amine.
A residence time of 10-15 minutes should be considered to be a
minimum value. In order to reduce the size of the vessel, the
normal liquid level can be set above its centerline.
Lean/Rich Amine Heat Exchanger
The lean/rich amine heat exchanger transfers heat from the lean
amine stream leaving the amine stripper to the rich amine being
fed to the stripper. It contributes to the energy efficiency of
the unit, since without it more heat would have to be added at
the stripper reboiler and more removed at the lean solvent
cooler. Lean/rich exchangers are designed with temperature
approaches between 35 0 Fand 50~. A rule of thumb is that if the
rich amine piping between the lean/rich exchanger and the
. stripper is carbon steel, the rich amine temperature leaving the
exchanger should be no greater than 215 0 F. If stainless steel
piping is. used in this section, however, higher temperatures can
be used without corrosion problems.
In most facilities, the lean/rich exchanger is a shell and tube
exchanger. The rich amine is generally the tube side fluid,
AMINE TREATING

2.23

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

while the lean amine is on the shell side. This selection is


made for two reasons: the rich amine becomes a two-phase mixture
as it is heated in the exchanger, and it is more important to
minimize the pressure drop of the lean amine. Plate and frame
exchangers have been used in some offshore amine units where
their lower weight and smaller size are significant advantages.
Amine stripper
Amine strippers or regenerators are distillation columns in which
CO 2 and H2S are driven out of the amine solution. They typically
contain between 20 and 25 trays. The rich amine enters the
column no lower than the fifth tray from the top. Amine solution
descends through the column and is stripped by steam rising from
the reboiler. The steam provides the energy to break the
chemical bonds between the amine and the acid gas. It also
drives the reaction equilibrium in the direction of regeneration
by carrying away the H2S and CO2 that are evolved from the amine.
Amine solution at the bottom of the column circulates through the
stripper reboiler. The reboiler generates the steam that serves
as the stripping gas in the column. A variety of reboiler types
can be used, including horizontal and vertical thermosyphons and
forced circulation reboilers. steam is the most widely used
heating medium, although hot oil is used frequently in upstream
plants. A few plants use direct~fired reboilers, although these
are not preferred due to the risk of overheating the amine and
causing degradation.
The purpose of the reboiler is to generate stripping steam.
stripping of the amine should take place on the first few trays
below the feed tray and not in the reboiler. The amine entering
the reboiler should be almost completely stripped of H2S and C02.
If it is not, acid gases will evolve from the amine in the
reboiler. This will cause rapid and severe corrosion in the
reboiler, reboiler return line, and the lower section of the
stripper. Inadequate stripping of the amine in the column can
occur if trays in the stripper are damaged, if the rich amine
entering the column is too cold, or if the amount of boilup in
the reboiler is too low.
The trays above the feed tray serve as wash trays where refluxing
water removes vaporized amine from the rising steam and acid gas.
, Two trays are used in this section in most designs, although up
to five can be used. Some strippers do not use any water wash
trays at all. The acid gas and steam exits the top of the
stripper and passes through the overhead condenser. This cooler
cools the stream to 100-130 o Fand condenses the steam in the
overhead stream. The mixture then enters the reflux drum, where
separation of the acid gas and condensed water takes place. The
AMINE TREATING

2.24

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

acid gas goes to sulfur recovery, flare, or vent, depending on


the amount of sulfur it contains and terms of the facility's
emissions permits.
In order to minimize reboiler energy requirements and amine
degradation rates, the stripper should be operated at the lowest
possible pressure. Most strippers operate with overhead
pressures between 10 and 20 psig. An overhead pressure
controller should be used to ensure steady operation of the
stripper as well as the downstream SRU if there is one.
The water in the reflux drum is returned to the stripper by a
reflux pump. Molar reflux ratios of 1:1 to 1.5:1 are typical.
The reflux ratio is determined by the boilup rate in the
. reboiler. A low reflux ratio indicates inadequateboilup in the
reboiler. This is a sign that the column is not operating
properly. If the amount of steam rising through the stripper is
inadequate, the amine will not be stripped of acid gas before
reaching the reboiler. As previously discussed, operation in
this mode will lead to corrosion problems.
Amine units treating gas produced in certain refinery operations
will pick up significant quantities of ammonia. This will
accumulate in the stripper reflux drum in the form of ammonium
bisulfide. In order to control the buildup of this material, a
sour water purge must be taken. Chevron practice is to operate
with a purge rate high enough to keep the concentration of
ammonia in the reflux drum below 1.0 wt%. This sour water may be
processed in a sour water stripper associated with the amine
unit, or it may be routed to a sour water treating system
elsewhere in the refinery.
Pumps
There may be two sets of pumps for the lean amine solution: the
booster pumps and the circulation pumps. The booster pumps pump
the lean amine solution leaving the stripper. They provide
enough head to get the amine solution through the lean/rich
exchanger, the lean amine cooler, and the filters. These pumps
are usually designed for discharge pressures of less than 100
psig. The circulation pumps pressurize the lean amine for high
pressure absorbers. They are often two-stage pumps, since the
lean amine comes to them from the surge tank at close to
atmospheric pre~sure. Refineries will often perform both
functions with a single pump.
Lean Solvent Cooler
The lean amine cooler cools the amine to the temperature at which
it is fed to the absorber. The temperature of the amine leaving
AMINE TREATING

2.25

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

this exchanger should be 10-lSoFabove the temperature of the gas


entering the absorber. If the amine is cooler than the gas,
hydrocarbons may condense and cause foaming. The amine and gas
temperatures should be measured as close as possible to the
absorber.
In amine units where MDEA is used to remove H2S selectively, the
performance of the unit will be very sensitive to the temperature
of the amine entering the absorber. A temperature change of SOF
will have a significant effect on the amount of CO2 that is
absorbed. More CO2 removal may increase the temperature of the
gas above the top tray, which will increase the equilibrium
concentration of H2S in the gas. As a result, close control of
the amine temperature at the outlet of the lean amine cooler is
essential.
Amine Surge Tank
The amine surge tank provides storage capacity for the amine
inventory in the plant. These vessels should be blanketed by an
inert gas to prevent oxygen from coming into contact with the
amine. Make-up water and amine are normally added in this
vessel.
Filters
Filters are used to prevent a buildup of particulates in the
amine stream. It is necessary to remove suspended particulates
which can increase erosion, corrosion, foaming and equipment
plugging. Most of the particulates enter the system with the
feed gas and collect in the amine. Filters may be located in the
rich amine downstream of the flash drum where they will do the
most good to protect the lean/rich exchanger and stripper (see
section 3.9). Typically the filters are located on the lean side
where the filter elements can be changed with minimal risk of
exposure to H2S.
It is preferred to filter the entire amine stream, although some
plants are designed for slipstream filtration. Bag, sock,
cartridge, and mechanical filters have been used. Bag filters
are recommended when the amine solution contains high levels of
particulates because they are less expensive and easier to
replace than the other types of filters. Sock filters have a
tendency to break when they fill with particulates.
The main advantage of mechanical filters is that the elements do
not have to be replaced regularly. Mechanical filters are used
on the amine plants at Gaviota and Carter Creek. These filters
use sheets of fine metal mesh as their elements. When the
differential pressure reaches 10 psi, the filters are
AMINE TREATING

2.26

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

automatically backwashed with amine solution. The amine is


routed to a cone-bottomed backwash tank, where most of the
particulates settle to the bottom. Solvent from the backwash
tank is returned to the amine storage tank. Gaviota uses a sock
filter on the amine leaving the backwash tank to remove any
particulates left in the amine. Both Gaviota and Carter Creek
have been pleased with the performance of these filters.
Particulate filters should remove all particles greater than 5-10
microns in diameter. Filters with an absolute rating of 5 or 10
microns should be used. An absolute rating means that the filter
will remove over 99% of the particulates greater than the rated
size from the solution.
(Vendors also use a IIrelative" rating
for filters; these remove a smaller percentage of the
particulates greater than the rated diameter from the solution.)
If the amine contains too many particulates, it will be very
difficult to use 5-10 micron-rated filters because they will plug
very rapidly. In these instances, filters rated for 25 micron or
larger particles should be used for a brief period. Once these
filters begin to last for a reasonable length of time, they
should be replaced with filters rated for slightly smaller
particles. By working down in this manner, filters rated for 5
or 10 micron particles can be installed eventually.
Activated Carbon Beds
Activated carbon is used to remove dissolved hydrocarbons and
other organic impurities from the amine solution. Normally, a
slipstream of 10% to 20% of the circulating amine should pass
through the carbon filter. An additional particulate filter may
be added downstream of the carbon bed to remove any carbon fines
that may be entrained by the amine passing through the carbon
bed.
The carbon will eventually become saturated with organic
impurities and stop removing any more of them from the amine
solution. Unlike the particulate filters, the differential
pressure across the carbon bed should not increase as the carbon
is spent. (If it does, this indicates that the particulate
filter is not doing its job and that the carbon filter is being
plugged by particulates.) The activity of the carbon filter must
be determined indirectly by analyzing the amine. The amine is
normally analyzed for hydrocarbon content; this will increase as
, the carbon bed becomes saturated. Many operators rely on a
visual inspection of the color of the amine entering and leaving
the bed to determine when it has become saturated. Once the
carbon bed is saturated, it can either be regenerated with steam
or replaced. It is estimated that steam regeneration will
restore only 80% of the original carbon capacity. After three
steam cycles, only 50% of original capacity is restored. So,
AMINE TREATING

2.27

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

three or four steam cycles are considered the limit before


replacing the carbon.

REFERENCES

2.1

Astarita, G., D. W. Savage and A. Bisio, Gas Treatinq with


Chemical Solvents, John Wiley & Sons, 1983, Chapter 15.

2.2

Kohl, A. L., and F. C. Riesenfeld, Gas PUrification, Gulf


Publishing Company, 1985.

AMINE TREATING

2.28

JULY 1994

FIGURE 2.1
TYPICAL AMINE PLANT FLOWSHEET

TREATED
(DR SWEET>

ACID
GAS
TO SRU

KNOCKOUT
DRUM

PARTICULATE
FILTER
WATER WASH
(FOR H2 PLANTS ONLY) ...
\-.(_---1

AMINE
COOLER

ACTIVATED
CHARCOAL
BED

HIGH PRESSURE
AMINE
CIRCULATION
PUMP

REGENERATOR
OVERHEAD
CONDENSER
REFLUX
DRUM

LEAN/RICH
EXCHANGER

ABSORBER
(DR CONTACTOR)

PURGE
STRIPPER
(DR REGENERATOR)

"50

STEAM
MAKE-UP
WATER
AND AMINE
REBDILER
FLASH
GAS

CONDENSATE

FLASH
DRUM

AMINE
CIRCULATION
PUMP
PARTICULATE
FILTER

HYDROCARBON

o
t'I-I

C\iLl.

W-I

a:c::(

S:E
ira:
o
z

9
LL

I. .J

a.

en

FIGURE 2.3

AMINE EQUILIBRIUM LOADING

20 WT% MEA AT 120 DEG F

~ 1.0E+02

oC/)
CJ 1.0E+01

o-1

,.,,.,.,--'''''~,,..,

EJ""".

,,..,,,,,,,,,,-8--,.......,,------

;;.r 1.0E+00
r::l.-" f::::l-.-"..-_eJ ,,,--,,,,,,-- "'t""..:J

C/)

a..

u.i 1.0E-01
a:

./""B"". . ..---

/'"

:::>

~ 1.0E-02
w
a:
a..
-1

1.0E-03

<l::

.-a:
<l::

1.0E-04

a..

~ 1.0E-05
CJ
~

<l::

1.0E-06

1 - '_ _--L-_

0.0

0.1

_- ' -_ _....L.-_ _- ' -_ _" ' - -_ _' - - - _ - - . l_ _----L_ _---I

0.2
0.3
0.4
0.5
0.6
0.7
LEAN LOADING, MOLS ACID GAS PER MOL AMINE

0.8

0.9

MEAlH2S MEAlC02

RVP
7/1/93

FIGURE 2.4

AMINE EQUILIBRIUM LOADING

-w 1.0E+02

30 WT% DEA AT 120 DEG F

()

C/)

(!J

1.0E+01

.....J

~ 1.0E+OO

C/)

0..

~ 1.0E-01
:::>
C/)
C/) 1.0E-02

w
a:
0..

.....J

1.0E-03

~~

I-

~ 1.0E-04
0..
C/)

1.0E-05

(!J

() 1.0E-06

0.0

0.1

0.2
0.3
0.4
0.5
0.6
0.7
LEAN LOADING, MOLS ACID GAS PER MOL AMINE
DEAlH2S DEAlC02
B
8

/;'-':1,.

0.8

0.9

RVP
7/1/93

'.

FIGURE 2.5

AMINE EQUILIBRIUM LOADING

-w

50 WTo/o MDEA AT 120 DEG F

~ 1.0E+02

()
(f)

C)

o.....I

/'.
1'.

1.0E+01

/'

;...----1....:

~ 1.0E+00

(f)

0..

ui 1.0E-01
a::

::>

~ 1.0E-02
w

a::

0..
.....I

1.0E-03

I-

a:: 1.0E-04

0..

~ 1.0E-05
C)

1.0E-06

--L-_ _- l -_ _.....L.-_ _- ' - -_ _.l...-_ _' - - _ - - - - J I . . . . . - _ - - - 1_ _- - '

L - '_ _

0.0

0.1

0.2
0.3
0.4
0.5
0.6
0.7
LEAN LOADING, MOLS ACID GAS PER MOL AMINE

0.8

0.9

MDEAlH2S MDEAlC02

RVP
711/93

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

3.0

SOLVENT CHARACTERISTICS

3.1

Amines

Alkanolamines are commonly used to remove HzS and COz (acid


gases) from a variety of gas and liquid streams. Some removal of
carbonyl sulfide (COS) and mercaptan sulfur (RSH) is also
possible. The most common generic amines are monoethanolamine
(MEA),. diglycolamine (DGA) , diethanolamine (DEA),
diisopropanolamine (DIPA), and methyldiethanolamine (MDEA). In
addition to these generic amines, several proprietary amines are
offered by solvent vendors. These proprietary amines are often
very pure forms of MDEA, blends of MDEA with other amines or
chemicals, or severely-hindered amines specially formulated to
achieve desired performance criteria such as H~S selectivity,
high capacity, deep removal, and low regenerat~on cost. Hybrid
solvents are sometimes used. These are blends of amines, which
react with the acid gas, and physical solvents, which absorb by
physical solubility only. Proprietary amines and hybrid solvents
will not be covered in detail in this guide. A table of physical
properties is provided in Table 3.1.1.
Chemistry: Amines are often described as primary, meaning one
hydrocarbon chain (R) attached to the nitrogen (RNHz); secondary,
with two hydrocarbon chains attached to the nitrogen (~NH); and
tertiary, having three hydrocarbon chains attached to the
nitrogen (R3N). MEA and DGA are primary amines; DEA and DIPA are
secondary amines; and MDEA is a tertiary amine. Because amines
form alkaline solutions with water, they can be used to absorb
acidic gases such as H S and CO. They all have the same basic
reaction chemistry with H2S. The following reaction with HzS is
considered to be instantaneous.
Acid-Base Reactions with HzS: (all amines, tertiary
shown, stoichiometry 1:1 HzS/amine)
H2S +

~N <===>

HS +

~mr

However, there are some differences between these amines when it


comes to CO reactions. All amines will undergo an acid-base
reaction wiEh CO2 The acid-base reaction of aqueous amines with
COz is much slower than the reaction with HzS. This may be a
benefit when it is desired to slip CO2 , but a disadvantage when
. complete COz remQval is desired. The overall reactions are:
Acid~Base

Reactions with CO~ to form bicarbonate (all


amines, tertiary shown, sto~chiometry 1:1 COz/amine)
CO2 +

SOLVENT CHARACTERISTICS

~N

+ H20 <===> HC03 + ~mr + OH


3.1

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

The further acid-base reaction to carbonate does not


proceed to an appreciable extent due to the solution
pH:
HC03-

+ R3N <===> C03= +

~NH+

In addition, primary and secondary amines can react directly with


the CO 2 to form carbamates. This is the predominant reaction at
loadings below 0.5 m/m (mole acid gas per mole amine), and it
occurs at a faster rate than the acid-base reaction for CO2
Carbamate Reaction with CO~ (primary and secondary
only, secondary shown, sto1chiometry 1:2 CO2/amine)
CO 2 +

2 ~NH

<===>

~NH2+

+ ~NCOO-

It is by this carbamate pathway that primary and secondary amines


are more reactive to CO2 although loadings are less due to the
1:2 stoichiometry. Because tertiary amines cannot form
carbamates, they react more slowly with CO2 via the acid-base
reaction. This feature has been exploited to provide absorption
'selectivity for H2S over CO2 By using a tertiary solvent such
as MDEA and shorter contact times, proportionally more H2S will
be absorbed, .providing savings in circulation rate and
regeneration duty. The carbamate reaction is also one of the
primary pathways to amine degradation with secondary amines
generally being more stable than primary amines.
Carbonyl Sulfide (COS) undergoes reactions with amines analogous
to those for CO above. The reaction rate with COS is even
slower than that for CO 2 (about 1/100), and COS reacts at a
faster rate with primary amines than it does with secondary
amines. The formation of a thiocarbamate is why primary and
secondary amines are better at absorbing COS than tertiary amines
and is also why COS-enhanced amine degradation is more of a
problem for these amines. with secondary amines, a significant
portion of the COS is hydrolyzed to form H2S and CO 2 and a
smaller amount participates in degradation reactions.
3.2

Performance

Amine Comparisons: Primary amines are stronger bases than


secondary amines which are stronger bases than tertiary amines.
This is why for equal acid gas loadings at equal temperatures,
the equilibrium partial pressure of an acid gas above the amine
will have the following trend: MEA < DGA < DEA < MDEA. Primary
amines, especially MEA, are best suited to low pressure 100
psi) applications which have fairly stringent acid-gas removal
specifications. On the other hand, the heat of reaction, which
SOLVENT CHARACTERISTICS

3.2

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

affects reboiler duty, follows the opposite trend: MEA, DGA > DEA
> MDEA (see Table 3.2.1). Reboiler duty is composed of three
components: sensible heat, latent heat of vaporization, and heat
of reaction.
Table 3.2.1:

Soln strength
Wt%

Typical Operating Conditions

MEA

DGA

DEA

DIPA

MDEA

15-20

40-60

25-35

20-40

45-55

Max. Rich Loadings,


m/m HzS or total
m/m CO z only (3)

S.40
.30-.35

S.50
.30-.40

S.50
.35-.40

S.50
.35-.40

Max. Lean Loadings,


m/m (3)

.10-.15

.08-.10

.05-.07

.04-.06

.004-.010

Heat of Reaction,
Btu/lb HzS (1,2)

550

674

511

526

522

Btu/lb co z (1,2)

825

850

653

703

600

Notes:

.45-.50
.40-.45

m/m = moles acid gas/mole amine


heat of reaction for loadings below 0.5 m/m (1)
sources: (1) Polasek, 1985; (2) TPA, 1991;
(3) DuPart, 1991.

solution strength: In general, the corrosivity of aqueous amine


solutions is highest for the primary amines and lowest for the
tertiary amines. Because of differences in solution corrosivity,
the higher order amines tend to be used at higher concentrations,
the exception being DGA. This results in more moles of amine per
gallon of circulating solution as seen by:
amine steangth
15 wt% MEA
30 wt% DEA
40 wt% DIPA
50 wt% MDEA
60 wt% DGA

lbmoles/gal
0.021
0.024
0.025
0.036
0.049

The rich acid-gas loadings tend to be somewhat higher too. The


net result of these two factors is that tertiary amines generally
require less circulation for a given amount of acid-gas
absorption thus saving pumping cost, regeneration cost, and
capital cost (smaller equipment).
SOLVENT CHARACTERISTICS

3.3

JULY 1994

Table 3.1.1: Physical Properties of Amines

'.

Secondary Amh>.~s

Primary Amlnes

Tertiary Amlnes

monoethanolamine

diglycolamine

diethanolamine

diisopropanolamine

methyldiethanolamine

MEA

DGA

DEA

DIPA

MDEA

Formula

HOC2H4NH2

HOC2H40C2H4NH2

(HOC2H4)2NH

(CH3CH(OH)CH2)2NH

(HOC2H4 )2NCH3

Mol. Wt.

61.1

105.1

105.1

133.2

119.2

339

430

516

480

477

Spec. Gravity, 60F

1.018

1.058

1.095

0.999

1.043

Specific Heat, Btu/lb-F

0.608

0.571

0.60

0.69

Thermal Cond.,
Btu/hr-ft2-F @ 77F

0.147

0.124

0.111

0.111

0.0906

Viscosity, cP .77F

18.9

26

352@86F

870@86F

173

Surf. Tension,
dyne/cm 77F

49.9

58.6

102.9

101.5

100.5

Heat of Reaction,
Btullb acid gas, H2S

-550

-674

-511

-526

-522

-825

-850

-653

-703

-600

15-25

40-60

25- 35

20-40

45 - 55

0.50

0.50

0.45 - 0.50

Solvent
Short Name

b.p, F

CO2
wt.% Range

0.60

. Loadings, m/m
Rich, H2S or Total

0.40

0.50

Rich, CO2

0.30 - 0.35

0.30 - 0.40

0.35 - 0.40

0.35 - 0.40

0.40 - 0.45

Lean, Total

0.10-0.15

0.08 - 0.10

0.05 - 0.07

0.04 - 0.06

0.004 - 0.010

0.47

0.94

1.45

Cost, $lIb (99%


truckloads, TX 4/94)

0.46

0.90

source: Dow Alkanolamines Handbook; Gas Conditioning and Processing, Vol. 4, R.N. Maddox, Campbell Petroleum Series; and HYSIM.

Page 3.3a

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Hydrocarbon Solubility: The greater the number of alkyl groups


(-CH?-, -CH3 , etc.) and the fewer the number of hydroxyl groups
(-OH) present on an amine molecule, the greater will be the
hydrocarbon solubility in the amine solution and the greater the
solubility of the amine in a liquid hydrocarbon stream. Hydroxyl
groups suppress hydrocarbon solubility while increasing water
solubility and reducing vapor pressure due to hydrogen bonding.
Based on this group-contribution argument, the expected trend in
hydrocarbon solubility (highest to lowest) is: DGA > DIPA > MDEA
> DEA, MEA.
Keep in mind that hydrocarbon solubility is also a
strong function of amine strength. Higher amine concentrations
give rise to higher hydrocarbon solubilities.

H2S Selectivity: As stated above, tertiary amines are unable to


form carbamates with CO2 CO2 is only absorbed via the
relatively slow acid-base reaction pathway. This slower CO2
reaction rate with tertiary amines allows them to slip more CO2
and absorb a higher proportion of H2S than primary and secondary
amines. Selectivity is improved by lower temperatures and short
contact times. The higher the temperature the faster the CO2
reaction rate becomes. Use of short contact times (shallow
weirs, fewer trays) limits the time available for CO2 reaction.
Keep in mind that the reaction rate for H,S is instantaneous, and
absorption i~ limited by mass-tr~nsfer rates. CO2 absorption is
generally limited by reaction rates.
Hindered amines also show good HS selectivity. Hindered
secondary amines, such as DIPA, have bulky hydrocarbon groups
which block easy access of CO~ to the nitrogen thus slowing
carbamate formation and reduc~ng its stability. FLEXSORB, an
expensive proprietary amine from Exxon, is a severely hindered
amine which shows excellent selectivity in low pressure
applications.
Deep CO2 Removal: In order to remove CO. down to very low levels
100 ppmv) , MEA is the generic amine of choice since it provides
the lowest partial pressure of acid gas for a given loading. The
solvent vendors all have proprietary blended amines which offer
deep removal and increased acid-gas capacity (scf/gal). These
are often blends of MDEA and MEA or DEA. Activated MDEA, offered
by BASF, uses piperazine as the "activator" for increasing cO2
absorption capacity.
COS Removal: Primary and secondary amines are reactive to COS.
The drawback is that they are also, to a certain extent, degraded
by COS. For MEA, 20% of the absorbed COS undergoes an
irreversible degradation reaction, and therefore MEA is not
advised for high COS service. For DGA, the degradation products
are substantially reversed at high temperature in the reclaimer.
COS removal by DGA increases with increasing DGA temperature and
SOLVENT CHARACTERISTICS

3.4

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

contact time. Removals as high as 75% or more can be achieved


(Moore, 1985). DEA undergoes some minor degradation. DIPA has
been reported to have severe, irreversible degradation with COS
(Astarita, 1983), but others claim only slight degradation
(Butwell, et al.,) which is probably the case. Shell offers a
hybrid solvent (Sulfinol D) using DIPA for the purpose of
enhanced COS removal. Use of long-contact-time polishing columns
using hot, very lean amine have been recommended for COS removal.
The goal here is to first remove H~S and CO2 which, being
stronger acids, can displace absorbed COS. The higher
temperature and longer contact times speed the reaction rate and
absorption. Once COS is absorbed, a portion of it is hydrolyzed
to H2S and CO2
RSH Removal: DGA is the most effective of the common generic
amines at methyl and ethyl mercaptan removal with reports of up
to 65-75% (Texaco). This is mostly due to DGA's higher
hydrocarbon solubility. Mercaptans are only slightly acidic, and
reactive absorption into alkaline amine solutions is poor. But
due to the hydrocarbon chain on the mercaptan molecule, they are
more readily absorbed by physical solubility. The other amines
only offer partial mercaptan removal. For absorption by MEA and
DEA, 40% to 55% removal of methylmercaptan, 20% to 25% removal of
ethylmercaptan, and 0% to 10% removal of propylmercaptan have
been reported (Butwell, et al.,). Hybrid solvents, because of
their physical solvent component (sulfolane in the case of
Shell's Sulfinol), are sometimes used for mercaptan removal.
3.3 Solution Quality

Poor solution quality will lead to a variety of problems:


excessive solution losses due to foaming and amine degradation,
excessive corrosion rates, equipment fouling and plugging,
excessive filter changeouts, excessive circulation rates and
regeneration duty, offspec performance resulting in shut-in
production and possibly environmental permit exceedances. If
poor solution quality is maintained in an amine plant, expect
high operating and capital costs to result. Poor performance by
the amine plant can also impact other unit operations adversely.
Downstream compressors can be damaged by amine carryover. Claus
sulfur-recovery unit catalyst can be harmed by excessive
hydrocarbon in the acid gas. Hydrotreater catalyst life can be
reduced over time by high H2S
The philosophy for designing and operating anamine plant, or any
plant for. that matter, is to solve the causes of problems not
just treat the effects. For instance, if a unit begins to
consistently foam, treat with antifoam injection to solve the
immediate problem and then determine and correct the cause of the
foam. In this chapter several problems associated with poor
SOLVENT CHARACTERISTICS

3.5

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

amine-solution quality are described as to causes, consequences,


and correction. By understanding the issues governing aminesolution quality, proper decisions can be made in plant operation
which will minimize these problems.
This understanding should
also be used in the design of new plants or in the retrofit of
existing plants in order to minimize some of the root causes of
poor amine-solution quality.
Contaminants: Amine solutions can become contaminated by a
variety of chemicals. Most of these contaminants are harmful to
~he solution because they cause foaming, enhance amine
degradation, or cause corrosion rates to increase. They should
be prevented from entering the system if at all possible; and
once in, should be managed at tolerable levels. These topics
will be covered in subsequent sections.
Table 3.3.1:

Common Amine Solution contaminants

treatment chemicals
hydrocarbon
particulates/scale
oxygen
carbon monoxide
organic .acids
ammonia
salts

foaming
foaming
erosion, foaming
degradation, corrosion
degradation
HSS, corrosion
no harm
corrosion

Ammonia is not harmful to amines; it is expelled in the stripper


overhead (Kohl, 1985). However, sometimes ammonium salts can
form in stripper overheads. (See "Amine Stripper" in section 2.4
and "General Corrosion" in section 4.1).
Table 3.3.2:

Some Recommended Maximum contaminant Levels

Particulates
Chlorides
Hydrocarbon
HSS
Iron
Degradation prod.

SOLVENT CHARACTERISTICS

200 mg/l
500 ppmw
0.1 wt% oil & Grease
by freon extraction (Coastal)
10 wt% of total amine complexed.
(see HSS section 3.5)
25 ppmw
no spec.

3.6

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

3.4

Amine Degradation

Consequences: Amines can undergo both thermal and chemical


degradation to create byproducts which may promote fouling,
corrosion and foaming (Meisen, 1993). Corrosion occurs due to
the acidic or chelating nature of some of the products (Chakma,
1986; TPA, 1991). Higher solution viscosities caused by
degradation products may lead to pumping and heat exchanger
problems (Meisen, 1993) as well as reduced mass-transfer
efficiency. Higher circulation rates may be required in order to
circulate the same quantity of active amine thus leading to
increased erosion/corrosion and higher pumping and regeneration
costs.
Thermal degradation: The rate of thermal degradation increases
with increasing amine concentrations and temperatures. In order
to minimize thermal degradation, (Bacon, 1987) offers the
following maximum guidelines:
Bulk temperature
Tube skin Temp.
Heat flux

260F
350F
6,000 to 8,000 Btu/hr/ft2

A more recent paper by Dow recommends a maximum bulk amine


temperature of 255F and a heating medium with a maximum
temperature of 300F, (DuPart, 1991). Another source recommends
keeping heat exchanger skin temperatures below 400 F to 450 F,
preferably below 400 F (Simmons, 1991)
Chemical degradation: This degradation mechanism is caused by a
variety of contaminants, and different amines may be more or less
susceptible to chemical degradation. Primary and secondary
amines undergo chemical degradation in the presence of CO2 , COS,
and CS 2 while tertiary amines do not. (Kohl, 1985). This
degradation is accelerated by increasing CO2 , CS 2 ' and COS
content, amine strength, and temperature (Dawodu, 1989; Meisen,
1993). COS irreversibly degrades MEA while the degradation
product formed between DGA and COS can be thermally regenerated
in the reclaimer, often standard equipment for DGA systems.
Avoid use of MEA in high COS service. DEA undergoes some
degradation by COS (Meisen, 1993). Exxon, in a discussion the
1991 Lawrence Reid Conference, mentioned that CO will react with
amines to form formates, especially at high temperatures and pH.
All amines are subject to oxidative degradation but some are more
susceptible than others. Oxidative degradation products include
carboxylic acids, which form heat-stable salts (HSS) with amine
and ammonia (Bradley, 1987: Pauley, 1988). Tests at CRTC showed
the following resistance to oxidative degradation: MDEA > MEA >
DEA (Manning, 1988; Robb, 1990): these test trends were confirmed
SOLVENT CHARACTERISTICS

3.7

JULY 1994

"-,

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

by Dow (DuPart, 1991). CRTC also showed that some of the


formulated MDEA-based solvents are more susceptible than generic
MDEA. Oxygen can also react with H2S to form sulfur species
which can contribute to corrosion as well as react with the amine
to form HSS (Kohl, 1985). It is very important to exclude oxygen
from amine systems by inert blanketing amine storage vessels and
eliminating leaks in vacuum vapor-recovery systems. HSS are
covered in more detail in section 3.5.
Degradation products and analysis: Individual degradation
products, other than HSS, can be determined by gas chromatography
and gas chromatographY/mass spectroscopy, although this requires
a specialized lab which has developed calibration standards for
the various degradation products. Total degradation products can
be determined by performing a Kjeldahl total-nitrogen analysis
and a total amine analysis. A comparison of total nitrogen with
amine nitrogen will give an indication of the degree of
degradation of the amine. Any ammonia absorbed from the feed gas
and not stripped out of solution will provide some error in this
analysis. A correction for thiocyanate is necessary if it is
present as a HSS.

SOLVENT CHARACTERISTICS

3.8

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Some Common Amine Deqradation Products: (Meisen, 1993)

OZD
HEI
HEED
BHEEU
BHEETU
HEOD
BHEP
THEED
BHEED
HEI
BHEI
HMPO
EG
HMP
DEP
HEP

product

source

oxazolidone
hydroxyethyl imidazolidone
hydroxyethyl ethylenediamine
diethanolurea
bis(hydroxyethyl)ethoxy urea
bis(hydroxyethyl)ethoxy thiourea
(both reversed in reclaimers)
N(hydroxyethyl)oxazolidone
(reversed to DEA by NaOH)
bis(hydroxyethyl)piperzine
Tri (hydroxyethyl) ethylenediamine
bis (hydroxyethyl) ethylenediamine
hydroxyethyl imidazolidone
bis(hydroxyethyl)imidazolidone
(hydroxymethylpropyl)oxazolidone
ethyleneqlycol
hydroxymethylpiperazine
Diethanolpeperazine
N(hydroxyethyl) piperazine

MEA-C02
MEA-COS
DGA-C02,COS
DGA-COS,CS 2
DEA-C02

DEA-COS
DIPA-C02
MDEA

Removal: High-boiling degradation products are removed by


distilling the amine overhead (see section 3.10 Amine
Reclamation). COS-induced degradation of DGA is reversible at
high temperatures and reclaimers are standard equipment on DGA
systems (Kohl, 1985; Moore, 1985, Meisen, 1993). Caustic
addition has been reported to reverse some DEA degradation
products such as HEOD (Meisen, 1993). The jury is still out on
how effective activated carbon is in removing degradation
products. Some say that it is not effective and that the carbon
quickly becomes saturated (Meisen, 1993). Others claim that some
degradation products are removed by activated carbon filtration.
Effective removal most likely requires distillation or purging.

SOLVENT CHARACTERISTICS

3.9

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

3.S Heat-Stable Salts


Definition: In aqueous amine systems heat-stable salts (HSS) are
the reaction products of organic and inorganic acids such as
formic, thiocyanic, and thiosulfuric and the alkanolamine.
Because these salt formation reactions are not reversed in the
higher-temperature amine regenerator, they are called heat
stable. Table 3.5.1 lists some of the common HSS-forming acids
found in amine systems and their chemistry.
Sources: Heat-stable salts and their precursors enter the amine
system in a variety of ways. Often the acids are carried into
the system in the inlet gas. Upstream processes such as cokers
and FCC's produce organic and inorganic acids as byproducts. If
these acids are not first removed from the gas, they will pass to
the amine unit where they will react and form HSS. Oxygen, if
present in the feed gas, will contribute to amine degradation
which can lead to the formation of formic as well as other acids
(Bradley, 1987). Oxygen can react with H2S to form thiosulfuric
acid via elemental sulfur (Kohl, 1985). If there is one single
step that will contribute most to maintaining a healthy amine
solution it would be adequate feed gas pretreatment by such means
as water washing, filter separators, coalescing filters, and
oxygen exclusion. Water washing the inlet gas will remove organic
acids formed in cracker units.
Consequences: HSS are detrimental to the operation of the amine
plant for several reasons. First, high levels of HSS are
associated with higher corrosion rates. Second, high HSS levels
are associated with more frequent foaming incidents. Foaming
tendency increases due to higher levels of corrosion-byproduct
iron sulfide particles which will stabilize foams. It is also
reported that high levels of organic acids which form HSS can
polymerize to form long-chain organic acids which cause foaming.
Third, HSS reduce the efficiency of the amine solution. Because
the portion of the amine in solution is bound by salt anions is
not available to react with acid gases such as H2S, higher amine
circulation rates are necessary.
Guidelines:

In general it is recommended that no more than 10


This is only a
guideline as every amine plant will differ (different salts,
hydrodynamics, temperatures, acid-gas loadings, etc.). Certain
HSS are worse than others, and recommended maximums for
individual species are given below. It is best to keep good plant
operating records on corrosion rates, HSS levels, amine strength,
loadings, and circulation in order to determine when HSS
reduction is necessary.
wt% of the circulating amine be bound by HSS.

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JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Maximum Recommended HSS Levels


Total HSS

10 wt% of total amine*

Formate
Acetate
oxalate
Glycolate
Thiocyanate
Thiosulfate

2000 ppmw in total solution


2000 ppmw in total solution
3000 ppmw in total solution

N/A
10,000 ppmw in total solution
10,000 ppmw in total solution

* This does not mean that 10X of the solution is HSS. It means, for example in the case of
100 lbs of 30 wtX DEA solution, that 3 lbs of DEA is bound by HSS and only 27 lbs of DEA is
available to react with acid gases. If all of the bound amine were bound to formate, the
concentration of formate in solution would be 13,000 ppmw or 1.3 wtX.

HSS Analysis: The determination of the different HSS-specie


concentrations requires ion chromatography (IC). IC analysis can
be provided by many of the solvent vendors. CRTC's analytical
lab also provides IC (contact: Mr. Muigai Karigaca,
CTN 242-3701). Potentiometric titrations and conductometric
titrations do not provide speciation but can be used to determine
total amine and bound amine. See the Monitoring Appendix for
details.
Removal Methods: There are several ways to remove HSS from
amines: purge and makeup, vacuum and steam distillation, ion
exchange, and electrodialysis. Purge and makeup may be the least
expensive option for small systems. The main costs are the price
of fresh amine and the disposal costs of the degraded amine. The
other options are dealt with in more detail in the section 3.10
on reclaiming amines and in the HSS Best Practices Guide.
As a temporary stopgap measure, caustic addition is sometimes
used to reactivateamines. While caustic does not actually
remove any salts, caustic, being a stronger base than the amine,
frees up bound amine by substituting sodium for the amine portion
(cation) of the salt. There are limits to how much caustic can
be added; Union Carbide recommends a maximum of 1.5 wt%. Too
much caustic can cause salt precipitation, especially sodium
oxalate, and reduced amine performance. There are conflicting
reports as to whether the sodium form of HSS formed by caustic
addition are more or less corrosive than the amine form of HSS.
MPR reports sodium-HSS to be as or more corrosive than the amineHSS (Mecum, 199~). Union Carbide disagrees. Chevron's
Pascagoula refinery has found that adding caustic to their DEA
system re~ulted in a reduction in laboratory measured corrosion
rates. The sodium-bound HSS still remain in the system and these
must eventually be removed either by reclaiming or by purge and
makeup. Guidance on caustic addition is provided in the HSS Best
Practices Guide.
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

TABLE 3.5.1:

HEAT-STABLE SALTS/ACIDS

Reaction with amine:


amine:

Am = RNH 2 ,

Heat-stable Salt
Precursor Acid:

HSSH

HSSH +

Am

<--->

~NH,

or

~N

= RCOOH, HSCN, H2S20 3 , etc.

AmH+ + HSS

Neutralization with caustic:


NaOH +

+ HSS <--->

Am

+ Na+ + HSS + H20

ACID

FORMULA

Ko1Wt

n))p C

pita l/plta 2
@ 2SC

Formic

HCOOH

46.03

100.7

3.75

Acetic

CH~COOH

60.05

117.9

4.75

Propanoic
(propionic)

CH3CH2COOH

74.08

141. 0

4.87

Glycolic

HOCH,COOH

76.05

decomp.

3.83

n-Butanoic
(n-butyric)

CH3C2H4COOH

88.12

163.5

4.81

Oxalic

HOOCCOOH

90.04

157

1.23/4.19

subl.
Benzoic

CAHJ;COOH

122.13

249

4.19

Thiocyanic

HSCN

59.09

decomp.

-2

Thiosulfuric

H,S,O~

114.14

---

.6/1.74

Sulfuric

~SO.'.

98.08

338

-3/2

Hydrogen
Sulfide

~S

34.

-60.4

7/12.9

CO2
Carbonic Acid

H2C03

62.

-78.5

6.3/10.3

ACID GASES

SOLVENT CHARACTERISTICS

as

3.12

CO~

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

3.6 Foaming

Indications: Foaming in amine systems can result in offspec


treated gas as well as high losses of amine solvent. Foaming is
first indicated by high and/or fluctuating pressure differential
(delta P) across the scrubber trays or packing (flooding is also
indicated by these signs). Severe foaming will be indicated by
high carryover of amine to the absorber knockout drum, a drop in
level or bouncing liquid levels in the columns and flash drum,
and erratic feed to the stripper (Stewart, 1991). Offspec gas
will likely result. When the delta P, in feet of water, is
greater than 40% of the height between the bottom tray and the
top tray, the scrubber is probably foaming (Lieberman, 1987).
Causes: Foaming can be caused by condensed or dissolved
hydrocarbon in the amine, lube oils from gas compressors,
treatment chemicals such as corrosion inhibitors or excess foam
inhibitors, fine particulates, amine degradation ~roducts,
organic acids of heat-stable salts, and detergents (Pauley, Dec
1989, July 1991). These contaminants reduce the surface tension
of the amine solution or, in the case of fine particulates, help
to stabilize foams. Poor operation of the flash drum will leave
excessive amounts of hydrocarbon in the amine leading to foaming
in the stripper and high hydrocarbon content to the SRU.
Prevention: A properly designed and maintained inlet filter
separator will do much to remove entrained liquids and
particulates from the gas prior to its entering the absorber.
For aerosols a coalescing filter is necessary. Maintain lean
amine temperature at least 10F to 15F above the feed gas
temperature to minimize condensation of hydrocarbons. This delta
T may have to be higher if a significant portion of the feed gas
. consists of acid gas as the dew point temperature increases as
acid gas is absorbed. Full flow mechanical filtration of the
circulating amine should be installed and properly maintained
(see section 3.9 Filtration for more details). Beware that
certain raw cotton or unwashed fabric elements may cause severe
foaming when first placed in service due to oil or soap coatings.
TPA recommends using virgin spun white cotton. Activated carbon
beds should be installed and properly maintained on a slipstream
of at least 10-20% of the circulating amine. Carbon fines, if
not backwashed from the bed before being placed in service, can
cause severe foaming. Mechanical filters should be placed both
upstream and downstream of the carbon bed (see section 3.9
Filtration). When any new equipment is installed, be sure to
thoroughly wash all oils and detergents from the equipment prior
to startup or severe foaming may occur. At least a 10-15 minute
rich amine residence time in the flash drum is recommended to
separate hydrocarbon from the circulating amine. As long as 30
minutes rich amine residence time in the flash drum has been
SOLVENT CHARACTERISTICS

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

recommended for MDEA service (TPA, 1991). Vessel interface


hydrocarbon skim taps, when installed, should be used at the
first sign of a free hydrocarbon layer.
Foam Inhibitors: Foam inhibitors or antifoams are sold by
several vendors (Betz, Nalco, VWR, Coastal, Union Carbide).
These consist of silica, silicone, high-boiling alcohol and
polyglycol based chemicals. The vendor can help select an
effective antifoam agent for your system. When foaming occurs,
give the system a shot of antifoam, preferably just upstream of
where the foaming is occurring. If foaming is a recurring
problem, it becomes necessary to determine the cause. Keep in
mind that adding too much of some antifoams, such as silicone,
can actually make foaming worse. Furthermore, some antifoams
such as the silicone-based ones are removed by the carbon filter
and overdosing will lead to premature depletion of the carbon.
Foam Test: A simple foam test should be done periodically to
determine the foaming tendency and foam stability of the amine
solution. It involves sparging air through an amine sample and
measuring foam height (tendency) during air flow and foam
collapse-time (stability) after stopping the air- flow. If the
lean amine shows low foaming tendency and stability while the
rich solution foams badly, poor inlet separation or insufficient
delta T is indicated. If the amine solution foams equally bad on
either side of the carbon filter, the carbon is spent and needs
to be replaced (Pauley, July 1991). Use a foam test to select an
effective antifoam chemical.
3.7

Losses

In an excellent paper by Dow Chemical Co., five routes of amine


loss are identified: vaporization, solubility, mechanical,
degradation, and entrainment (stewart, 1991). The paper offers a
systematic approach to identifying the source of the losses and
reducing the losses.
First, total amine loss per MMscf of treated gas should be
estimated from data on past amine purchases and gas throughput.
Also, keep track of amine losses by monitoring tank and vessel
levels. Next, identify the primary routes of amine loss for your
plant. Then control those losses in the order of their
magnitude. Generally, the ranking of losses from highest to
. lowest in a gas plant is mechanical, entrainment, vaporization,
degradation. When a liquid treater shares the amine with a gas
absorber,-the ranking is mechanical, entrainment (in liquid),
solubility, entrainment (in vapor), vaporization, degradation
(stewart, 1991). Be warned that as the loss rate is reduced, the
purge rate of contaminant loss is also reduced. Expect an
increase in contaminant levels, and monitor and control these
SOLVENT CHARACTERISTICS

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

contaminants during the amine-Ioss-reduction process by adequate


mechanical and carbon filtration.
Vaporization Losses: Vaporization losses increase with
increasing top-stage temperature, increasing amine strength, and
decreasing pressure. The Dow paper includes graphs for
estimating vaporization losses for MEA, DEA, and MDEA. For a
typical fuel-gas absorber and flash drum, the estimated
vaporization losses in the overhead streams would be:
Vaporization Loss Estimates (stewart, 1991):

Pressure, psia
Temperature, of

Absorber
100
120F

Flash Drum
50
140F

Amine Loss. lb Amine/MMscf:


15 wt% MEA
30 wt% DEA
50 wt% MDEA

3.5
0.028
0.63

12
0.19
2.9

If the pressure were 1000 psia, the vaporization losses would be


about one tenth of these values. Vaporization losses from the
stripper are relatively small due to condensed-water reflux
containing only 1 to 5% amine and to low acid-gas flows.
Vaporization losses can be reduced by lowering the temperature of
the lean amine while still maintaining the 10 to 15F
differential above the feed gas temperature. Installing waterwash trays above the lean amine inlet is also very effective.
water wash trays on the flash tank vapor outlet may also be
advisable.
Solubility Losses: Solubility losses occur in amine treating of
liquid hydrocarbon streams such as LPG. These losses increase
with increasing temperature, decreasing pressure, and increasing
amine concentration. Because temperature and pressure are
maintained within narrow limits on an LPG treater, reducing amine
concentration is the primary solubility-loss control adjustment.
The Dow paper provides graphs of MEA, DEA, and MDEA solubility in
propane and butane at 77F and 300 psia. These graphs show the
benefit of reducing amine concentration. Reduction in amine
. concentration can't always be done when the amine is shared by a
gas treater. Water washing the treated LPG stream, as with gas
streams, is often used to recover dissolved amine. This is
especially necessary if DGA is used in a liquid treater due to
its high solubility in hydrocarbons.

SOLVENT CHARACTERISTICS

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Solubility of Amines in Liquid Propane and Butane (Stewart, 1991)


(77Op and 300 psia)
Solubility
in Propane
(ppmw)

Solubility
in Butane
(ppmw)

10
15

~% MEA
~% ~A

160
265

120
190

20
30

~%
~%

DEA
DEA

75
130

50
80

40
50

~%

MDEA
MDEA

160
300

95
180

~%

Entrainment in Vapor: This can occur through either a liquid-ingas dispersion (mist or aerosol) or a gas-in-liquid dispersion
(foam). Foaming and its control is covered in section 3.6.
Heavy mist entrainment is indicated by an overloaded treated-gas
knockout vessel: and for aerosols, buildup of amine in low spots
and in equipment downstream of the knockout. Causes of
entrainment are:
-

undersized tower diameter for gas flow


operation of tower below design flow
operating at or above flooding
plugged or damaged trays
undersized or damaged amine distributor
damaged mist eliminator pad
damaged knockout or undersized vessel

Installation of mist pads at the top of absorbers and knockout


vessels, either the wire-mesh or vane type, can help control mist
entrainment. The knockout vessel should be sized for surge flows
not average flows. If gas flows change, check that the vessel
and mist pad are still adequate.
Entrainment in Liquid: Formation of very small droplets of amine
solution within a liquid treater can lead to high losses when the
drops are too small to disengage from the liquid hydrocarbon.
For this reason liquid treaters are designed for low flows and
shear in order.to prevent the formation of small droplets and
emulsions. Loss of amine by this route is indicated by the
presence of amine in downstream filters and low spots in the
hydrocarbon stream. Check that the treater is operating within
the Chevron-recommended design parameters for distributor orifice
velocities and superficial velocities eLi and Wuopio, 1992).
Damaged or plugged distributors may be at fault. Provide a
SOLVENT CHARACTERISTICS

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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

gravity separator with enough residence time and low enough


velocity to disengage a 100 micron amine droplet. Coalescing
filters downstream of the separator will remove the smaller
droplets. A water wash does much to recover entrained amine.
Estimating Entrainment Losses: Close the knockout vessel dump
valve and measure liquid level vs. time to estimate the carryover
caught by the knockout vessel. Portable gas-testing equipment
can measure entrainment that passes beyond the knockout. A
coalescing-filter vendor such as Porous Media or ACS may be able
to provide this service. Taking a measured slipstream of gas
through a water wash, titrating the water for amine, and then
correcting for amine dissolved in the gas (vaporization loss)
will provide an estimate of liquid amine entrained in the gas.
Degradation Losses: Dow recommends estimating the rate of amine
degradation and HSS complexation by doing a rough species balance
on HSS and amine degradation products. Assume that the system is
in steady state. In other words, the rate of degradation is
equal to the rate of degradation product/HSS purge by physical
amine losses. Then, by their example, if the amine solution
contains 2 wt% degradation products and HSS while the amine
solution loss rate is one pound per hour, the active amine
degradation ~ate is 0.02 lb/hr. If this rate is high, determine
the causes (chemical or thermal degradation, organic acids in
feed'gas, etc.) and correct them.
Mechanical Losses: Dow writes that this is typically the largest
source of amine loss characterized by leaks, drips, and purge
streams. Sources are:
-

pipe flange/gasket connection leaks


pump seal flushes and leaks
pressure gauge and sample purge lines
frequent filter changeouts
filter cartridge elements
overhead fan-cooler tube leaks
water-cooler tube leaks
leaky amine dump valve

Mechanical losses are estimated as the difference between the


estimate for total amine losses and the estimated losses from
vaporization, entrainment, solubility, and degradation.
Individual mechanical losses are determined by plant inspection
and operating-procedure review. Control these losses by
repairing. leaks and routing purge and flush streams to the amine
sump tank. Flush the filters with condensate prior to changeout.
Before reintroducing amine from the sump back to the main system,
the amine should be filtered and the sump should always be under
nitrogen blanket.
SOLVENT CHARACTERISTICS

3.17

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Amine-Loss Guidelines: The average amine loss from a survey of


West Texas gas plants using MEA, DEA, and MDEA was 3 lb/MMscf of
treated gas. Because these were mostly high-pressure gas plants,
the vaporization losses were a minor component of the total loss
rate. For low-pressure refinery amine plants with water-wash
trays, the 3 lb/MMscf rate is achievable and losses in the range
of 1 to 2 lb/MMscf should be the goal. If water-wash trays are
not installed, add the estimated vaporization loss to the 1 to 2
lb/MMscf rate, and set that as a target to remain under. The
1991 MDEA User's Conference recommended a MDEA-loss goal of 2 to
4 lb/MMscf of treated gas.
Actual losses were usually 8 - 10
lb/MMscf and sometimes much higher (TPA, 1991). CUSA Products
uses a benchmark loss rate of 7-10 lb/MMscf.
3.8

Makeup water

Use high-quality condensate as makeup water to amine systems.


Dow's recommended water quality specifications are (Bacon, 1987;
DuPart, 1991):
Total Hardness
Total Dissolved Solids (TDS)
Sodium .
Potassium
Chlorides
Iron

(maximums)
3 gr/gal
100 ppm
3 ppm
3 ppm
2 ppm
10 ppm

Periodically check the water balance to determine if leaks are


occurring. Declining amine strength may indicate either a water
cooler is leaking, if the water pressure is higher than the amine
pressure, or a regenerator reboiler tube leak. High TDS in the
cooling water and high TDS in the amine may also indicate a
cooling water leak (Lieberman, 1987).
3.9

:Filtration

Filtration, mechanical and carbon, is necessary to remove


contaminates which promote foaming, corrosion, and erosion.
Mechanical filtration removes particulates while carbon
"filtration" removes dissolved contaminants. Proper installation
. and maintenance. is important.
Mechanical Filters
Mechanical filtration on 100% of the amine circulation is
recommended to remove suspended particulates which can increase
erosion, corrosion, foaming, and equipment plugging. Many
SOLVENT CHARACTERISTICS

3.18

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

experts recommend filtration on the rich amine just downstream of


the flash drum as this will do the most to protect the stripper
from particulates picked up by the absorber (DuPart, 1991; TPA,
1991, Veldam, 1994). Rich amine filtration can be done safely if
adequate precautions are taken. Before opening the filter, a
lean amine wash, condensate wash, nitrogen purge should be done
followed by analyzing the vapor space to ensure that H~S levels
are below 10 ppmv. Before placing the filter back onl1ne, air
should be purged from the housing. Chevron's general practice is
with lean-side filtration due to safety concerns. A 5 or 10
micron "absolute" particle-size cutoff rating is recommended on
the filter elements.
Mechanical filters come in a variety of configurations:
cartridge, bag or sock, and automatic backflush. The first three
types use disposable elements of various designs and materials.
Some are expensive but offer high capacity, dimensional stability
under pressure, and ease of replacement. Beware of treated
cotton or fabric elements as these may contain surfactants which
will cause foaming upon startup. Follow the manufacturer's
recommendations for determining time to changeout. Generally
this is determined by pressure differential across the filter.
Look for filter elements or cartridges which have high removal
efficiency and capacity, are quick to change out, and easy to
dispose. Generally this means fewer elements will minimize labor
and disposal costs.
The automatic backflush designs are initially quite expensive,
but they save in filter replacement and disposal costs. At a set
pressure differential, these units are backflushed with clean
amine into a particle settling tank. After settling, the amine
is pumped through a conventional cartridge filter and back into
the system.
Vendors: There are many filter vendors.
short list; no recommendations are made.

SOLVENT CHARACTERISTICS

3.19

Table 3.9.1 contains a"

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Table 3.9.1:

Filtration Vendors

1. Cartridge, sock and bag filters are sold by:


CUNO Process Filtration, Inc.,
Meriden, CT
800-243-6894

Facet Enterprises, Inc.


Tulsa, OK
918-939-5451

Filterite Corp.
Timonium, MD
301-252-0800

Pall Corp.,
East Hills, NY
800-645-6532

Rosedale Products, Inc.,


Ann Arbor, MI
800-821-5373

3-M Corp.
st. Paul, MN
800-648-3550

2. Automatic-backflush filters are sold by:


Vacco Industries
EI Monte, CA
818-443-7121

Ronnigen-Petter
Portage, MI
616-323-1313

Coastal Chemical Company


Houston, TX
713-999-6182

3. Inlet Filter/Separators, Coalescing Filters:


ACS Industries
Houston, TX
800-231-0077

Burgess Manning
Dallas, TX
214-631-1410

otto York Co., Inc


Los Alamitos, CA
213-594-0984

Systems, Inc.
Houston, TX

~orta-Test

713-771-8961

Porous Media, Inc.


st. Paul, MN
612-653-2000
SOLVENT CHARACTERISTICS

3.20

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Carbon Filters
Carbon filtration is installed to remove dissolved hydrocarbon
and possibly some amine degradation products from the circulating
amine by adsorption (Simmons, 1991). It does not remove heatstable salts but may remove HSS precursors (Bright, 1987; TPA,
1992). Carbon beds are often very effective at removing
corrosion and foam inhibitors.
Carbon filtration on a minimum of 10-20% slipstream is
recommended. A general rule of thumb is to filter as large a
slipstream as you can afford. Carbon beds should be placed on a
cool, lean amine slipstream to prevent acid-gas binding of the
bed, for improved filtration efficiency, and for safety reasons
{Bacon, 1987; Calgon; Pauley, July 1991). The carbon bed should
be protected upstream by a mechanical filter as carbon beds will
also remove particulates which would shorten the life of the bed.
A mechanical filter downstream of the carbon bed is necessary to
remove any carbon fines which can cause foaming. Carbon bed
should be provided with 2 to 4 gpm flow per square foot of
crossectional bed area, (TPA, 1991; Calgon, 1983; Pauley, July
1991). Flow should be top to bottom and recommended residence
times vary from 10 to 30 minutes (Calgon, 1983; Bright, 1987).
Lignite carbon, having a mesh size of 8 x 30 or 4 x 10, is
reported to have superior performance to wood-based, bituminous
or sub-bituminous carbon (TPA, 1991). Determine time for
changeout by inlet and outlet amine analysis (foaming
tendency/stability, color, and hydrocarbon content) not by
pressure differential. The carbon may become spent well before a
noticeable pressure differential is seen. High pressure
differential may indicate improper installation of the carbon or
bridging/clumping of the carbon bed. Spent carbon is generally
returned to the vendor for regeneration and resale.
3.10 Reclaiminq

The subject of reclaiming degraded and contaminated amines is


covered in detail in the HSS Best practices Guide. This guide
describes and gives guidelines for choosing the best reclaiming
option for a particular plant and amine solution. Proper choice
will depend on system volume, amine type, and nature and
concentration of the contaminants. The following options are
available and so~rces of these services are given in Table
3.10.1.
Distillation: Distillation will remove both HSS and high-boiling
degradation products and contaminants, and particulates. caustic
is added to first neutralize the HSS. MEA and DGA systems often
have thermal reclaimers installed. These are basically small
SOLVENT CHARACTERISTICS

3.21

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

atmospheric distillation units. MEA reclaimer bottoms


temperature is typicallY around 280F, and with steam sparging
DGA reclaimers maintain a bottoms temperature of 360 to 380F
(Kohl, 1985). DEA and MDEA require vacuum distillation in order
to lower the reboiler temperature below the thermal degradation
temperature for these amines. Distillation does not remove all
degradation products. For instance BHEP is not removed from DEA
by vacuum distillation (Meisen, 1993).
Because distillation can remove more contaminants than just HSS,
if the amine solution contains a significant portion of
degradation products as well as HSS, then reclaiming by
distillation might be favored.
Some solvent reclaiming companies (Canadian Chemical Reclaimers
and Industrial waste Processors) bring a mobile distillation unit
to your site, process a solvent slipstream for a fee, return the
regenerated amine to the system, and leave the water and bottoms
sludge for the site to dispose (Millard, 1993). Others, such as
Romic, truck the amine to their own plant and then return the
reclaimed amine. Romic charges for transportation, water and
waste disposal, and then sells back the clean amine.
As recently learned at the Richmond Refinery through experience
with Romic, reclaiming amines by vacuum distillation occasionally
may not work for cleaning up amine solutions to the desired
quality, possibly due to the presence of unidentified
contaminates. Reclaiming service companies should be willing to
run bench-scale tests on samples of dirty amine. Also, detailed
laboratory analyses for HSS and other possible contaminants
should be run by Chevron or the service company before and after
reclaiming to determine the effectiveness of the cleanup.
Steam Stripping: In this process performed at essentially
atmospheric pressure, a large recycle stream of steam is used to
strip the amine overhead while maintaining a bottoms temperature
below the thermal degradation temperature of the amine.
Currently, this service is offered by Coastal Chemical at their
Abbeyville, LA site. Sometimes Coastal will swap previously
reclaimed amine for an amine plant's spent amine.
Ion Exchange: This HSS-removal process, performed onsite,
involves passing a slipstream of lean amine through a series of
ion-exchange beds to pullout cations such as Na+ and the typical
HSS anions. Charges are based on lbmoles of ions removed.
Unstripped H2S counts as an anion (HS), so it is important to
have the amine as lean as possible. The beds are periodically
regenerated with acid and caustic. The waste stream is an
alkaline solution of sodium salts which can generally be
processed by the effluent-treatment pond. Organic amine
SOLVENT CHARACTERISTICS

3.22

JU~Y

1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

degradation products are not removed by ion exchange.


In addition to charges based on the number of pound moles of
salts removed, there are charges for mobilization and delays not
caused by the vendor (MPR). The site incurs costs for
regeneration chemicals, tank and truck rental, site preparation
and supervision, and waste handling.
Electrodialysis:
This is a membrane-based HSS-removal process
called UCARSEP offered by Union Carbide. It does not remove
organic degradation products. With this process an electric
field drives HSS anions through a membrane in order to remove
them from the amine solution. An aqueous salt stream is the
waste product .

SOLVENT CHARACTERISTICS

3.23

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Table 3.10.1:

SOURCES OF RECLAIMING SERVICES

Ion-Exchange Processes
MPR Services
4600 Park Road, suite 300
Charlotte, North Carolina
Contact: Mr. Shade Mecum
(704) 523-8282

26209

Vacuum Distillation
Romic Chemical, Company
2081 Bay Road
E. Palo Alto, California 94303
Contact: Mr. Ron Tressen
(415) 324-1638, Ext. 525
Industrial Waste Processing
P.o. Box 1360
Lyman, Wyoming 82937
Contact: Mr. Chuck Simmons
(307) 786-4914
Canadian Chemical Reclaimers
610 Prairie Meadows Close
Bound Brooks, AB T1R OC9 Canada
Contact: Mr. Todd Beasley
(403) 362-6229, Ext. 2005
Steam Stripping
Coastal Chemical Company, Inc.
363 North Sam Houston Parkway E.,
suite 380
Houston, Texas 77060
Contact: Mr. Ray Veldman
(713) 999-6182
Electrodialysis
Union Carbide Corp.
Gas Treating customer support Center
335 Pennbright Dr., Suite 120
Houston, TX 77090-5909
(800) 822-7765
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REFERENCES

Abry, R.G.F. and M.S. Dupart, "Amine Plant Troubleshooting and


Optimization: A Practical Operating Guide," presented at the
Lawrence Reid Gas Conditioning Conference, Norman, OK, March 1-3,
1993.
Astarita, G, D.W. Savage, and A. Bisio, Gas Treating with
Chemical Solvents, John Wiley & Sons, New York, 1983.
Bacon, T. R., "Amine Solution Quality Control Through Design,
Operation, and correction," presented at the Lawrence Reid Gas
Conditioning Conference, Norman, Oklahoma, March, 1987
. Bacon, T. R., "Monitoring the Efficiency of Amine Treating
Plants," presented at the Lawrence Reid Gas Conditioning
conference, Norman, OK, March, 1989.
Ballard, D. and S. A. von Phul, "Cut Filtration Costs by 80%,"
Chemical Eng. Prog., May 1991.
Bright, R. and D. A. Leister, "Gas Treaters Need Clean Amines,"
Hydrocarbon Processing, Dec. 1987.
Bradley, V. V. and S. P. oostwouder, . "Solvent Changes Improve
Amine Treating Operations," presented at the Lawrence Reid Gas
Conditioning Conference, Norman, OK, March, 1987.
Butwell, K. F., "Fundamentals of Gas Sweetening," presented at
the Lawrence Reid Gas Conditioning Conference, Norman, Oklahoma,
March, 1983.
Butwell, K.F., D.J. Kubek, and P.W. Sigmund, "Primary Versus
Secondary Amines - Characteristics in Gas Conditioning,"
publication unknown, Union Carbide Corp.
Calgon Corp. Technical Bulletin 23-61b, 1983.
Chakma, A and A Meisen, "Corrosivity of DEA solutions and their
Degradation Products," Ind. Eng. Chem Prod. Res. Dev., Vol 25,
No.4, 1986.
Dawodu, 0 and A. Meisen, "Amine Degradation by Carbonyl Sulfide
. and Carbon Disulfide," presented at the Lawrence Reid Gas
Conditioning Conference, Norman, Oklahoma, March, 1989.
Dawodu, 0., Meisen, A., Beasely, T, "Reclamation of Spent Amine
Solutions," presented at the AIChE Spring National Meeting,
Houston, Texas, March 28-April 1, 1993.
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

DuPart, M.S., T.R. Bacon, and D.J. Edwards, "Understanding and


Preventing corrosion in Alkanolamine Gas Treating Plants,"
presented at the Lawrence Reid Gas Conditioning Conference,
Norman, Oklahoma, March, 1991.
Keaton, M. M. and M. J. Bourke, "Activated Carbon System Cuts
Foaming and Amine Losses," Hydrocarbon Processing, August 1983.
Kohl, A and F. Riesenfeld, Gas Purification, 4th ed., Gulf
Publishing Co. 1985.
Li, G. and R. A. Wuopio, "Packed Liquid/Liquid Extraction Column
Design Guide", CRTC report dated June 22, 1992.
Manning, C, "Amine Degradation Study - 02/C02 Exposure Results,"
CRTC Report dated June 8, 1988.
Mecum, S. M., et al., "Heat-Stable Salt Removal From Amines by
the HSSX Process Using Ion Exchange," presented at the Lawrence
Reid Gas Conditioning Conference, Norman, Oklahoma, March 2,
1992.
Meisen, A. et al., "Reclamation of Spent Amine S'olutions," .
presented at the AIChE Spring National Meeting, Houston, TX,
March 28 - April 1, 1993.
Millard, M. G., and T. Beasley, "contamination Consequences and
Purification of Gas T.reating Chemicals Using Vacuum
Distillation," presented at the Lawrence Reid Gas Conditioning
Conference, Norman, Oklahoma, March 1-3, 1993.
Moore, T.F., J.C. Dingman, and F. L. Johnson; "A Review of
Current Dyglycolamine Agent Gas Treating Applications," in Acid
and Sour Gas Treating Processes, S. Newman, editor, Gulf
Publishing Co., 1985.
Pauley, C. R., R. Hashemi, and S. Caothien, "Analysis of Foaming
Mechanisms in Amine Plants," presented at the AIChE Summer
National Meeting, Dever, CO, August 21 - 24, 1988.
Pauley, C. R., R. Hashemi, and S. Caothien, "Ways to Control
Amine unit Foaming Offered," oil & Gas Journal, Dec. 11, 1989.
Pauley, C. R., D. G. Langston, and F. C. Betts, "Redesigned
Filters Solve Foaming, Amine-Loss Problems atLouisianna Gas
Plant," oil & Gas Journal, Feb. 4, 1991.
Pauley; C. R., "Face the Facts About Amine Foaming," Chemical
Engineering Progress, July 1991, p.33.
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Polasek, J. and J. Bullin; "Process Considerations in Selecting


Amines," in Acid and Sour Gas Treating Processes, S. Newman,
editor, Gulf Publishing Co., 1985.
Robb, D, "Amine Degradation Study - 02/C02/H2S Exposure Results,"
CRTC Report dated Feb. 28, 1990.
Simmons, C. v., "Reclaiming Used Amines and Glycols," presented
at the Lawrence Reid Gas Conditioning Conference, Norman,
Oklahoma, March 4-6, 1991.
Stewart, E. J. and R. A. Lanning, "A Systematic Technical
Approach to Reducing Amine Plant Solvent Losses," presented at
the Lawrence Reid Gas Conditioning Conference, Norman, OK, March
.4-6, 1991.
TPA, Inc., 1991 MDEA Conference Proceedings, May 1991.
Veldman, R; verbal from Coastal Chemical Co. Sales Director, 31
March 1991.
von Puhl, S. A. and C. D. Houston, "Common Amine/Glycol System
Problems and Solutions," Proceedings of the 72nd GPA Annual
Convention.

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4.0 CORROSION CONTROL

This chapter focuses on controlling amine corrosion in refineries


and large gas plants, where we design for long equipment lives.
Materials recommendations and other corrosion control measures
will not necessarily apply to small packaged units, which are not
designed for 20 - 30 years of service.
4.1

Corrosion in Amine Treating Plants

General Corrosion
The severity of corrosion in an acid gas removal plant strongly
depends on the operating conditions. The primary variables that
affect corrosion are temperature, heat stable salts, solution
strength, and acid gas loading. Solution cleanliness and
velocity are also important. The effect of these operating
conditions on corrosion is discussed in detail in section 4.2.
To a lesser extent, corrosion depends on the type of amine used
in the process. Chevron uses three types of amines for acid gas
removal: MDEA (methyldiethanolamine), MEA (monoethanolamine) and
DEA (diethanolamine). Regardless of the amine type, corrosion
often takes the form of a pitting or localized attack, especially
in turbulent areas. Degradation of the amine increases its
corrosivity.
Figure 4.1 shows potentially corrosive areas of an amine plant.
A section of the plant that characteristically corrodes is the
hot regenerator bottoms system. Attack may occur in the
reboiler, reboiler return line, lower portion of the regenerator,
hot amine piping, and rich/lean amine exchangers.
In CO 2 removal plants, carbonic acid corrosion can occur in
regenerator overhead systems, especially in turbulent flow areas.
Corrosion usually takes the form of very localized etching,
pitting or gouging. Carbonic acid corrosion can be mitigated by
adjusting process conditions, through use of the proper solvent
formulation and/or alloy upgrades. Generally, the remedy for
overhead condenser tube corrosion in cO2 removal plants is
upgrading to T-304 stainless steel. If air coolers are used,
inlet and outlet headers should also be stainless steel.
Regenerator overhead systems in H2S removal plants are
susceptible to corrosion when the nonvolatile inhibitor (if used)
and the alkaline amine are not carried overhead. Regenerator
overhead corrosion has increased with increasing use of high
nitrogen crudes because cracking or hydrotreating these crudes
produces cyanide and ammonia. Both are absorbed by aqueous
amines and concentrated in the regenerator overhead as ammonium
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bisulfide (NH4HS) and, often, excess ammonia. Alloy materials


may be required to avoid corrosion in the top of the regenerator.
In the overhead systems of plants processing hydrocracker, coker,
or FCC gases, experience indicates that stainless steels (Types
304 and 316) corrode at about the same rate as carbon steel.
Corrosion control measures in these plants include use of
ammonium polysulfide to convert cyanides to harmless
thiocyanates, reflux bleed streams to minimize buildup of NH4HS
in reflux loops, and titanium condenser tubes.
The reflux bleed stream (see Figure 4.1) allows removal of NH3
and control of NH4HS that would otherwise concentrate in the
overhead system. Ideally, NH4HS should be limited to a maximum
of 2% to 3%. This is often not possible, but reducing NH4HS to
even 5% to 10% is desirable. The reflux bleed piping also allows
purging of any hydrocarbon trapped in the overhead system.
Another alternative for control of NH4HS is to remove ammonia
from the gas before it enters the amine system. This can be
accomplished by washing the gas at a point of high turbulence
such as the entrance to a cooler.
cracking of Carbon Steel Equipment
Stress-Corrosion cracking
Amine solutions can cause stress-corrosion cracking of nonstressrelieved carbon steel. Generally, MEA will crack steel under
milder conditions (e.g. lower temperatures) than OEA or MOEA.
The industry has reported cases of MEA cracking down to ambient
temperatures and OEA cracking down to 140F. MOEA is considered
to be similar to DEA with respect to stress-corrosion cracking
and the existing database is not yet sufficiently developed to
discriminate these two amines.
Carbon steel in amine service is most likely to crack in areas of
the plant operating at the highest temperatures. stress
corrosion can occur both rapidly and extensively at regenerator
bottoms temperatures (240F - 280F), but becomes less serious as
the temperature decreases.
Water-washing equipment prior to shutdown steam-outs prevents
stress-corrosion cracking of nonstress-relieved equipment
operating at low temperatures during service. A water-wash with
distilled water or steam condensate will remove residual amines,
which can crack nonstress-relieved equipment when heated during
steam-out. Residual amines cracked a nonstress-relieved MEA
absorber column during a Chevron refinery shutdown in 1974.
The most reliable way to avoid stress corrosion cracking in amine
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service is to stress-relieve welds. Refer to Figure 3700-4 in


the Corrosion Prevention Manual for our current stress relief
guidelines for new construction. We recommend stress relief of
all new pressure vessels in amine service, regardless of
operating temperature. piping in amine service should be
stress-relieved if it operates above 100F. For socket and seal
welds in MEA service, use a flanged bonnet valve instead of a
welded valve, to allow removal of the valve during stress-relief.
In DEA and MDEA service, socket and seal welds 1-1/2 inches and
smaller do not require stress relief.
Table 4.1 gives inspection guidelines for existing plants where
original stress relief was not as extensive. From a technical
viewpoint, we do not consider it necessary to inspect DEA and
MDEA vessels operating below 150F, unless more than 50 ppm H2S
are present. In that case, refer to guidelines for wet H2S
cracking. For vessels previously in MEA service, inspect once as
an MEA vessel, regardless of its present service. Subsequently
inspect the vessel according to guidelines for its current
service.
When repairing stress-relieved piping or equipment in hot amine
service, it is necessary to stress-relieve repair welds to avoid
cracking. Vessels should be stress-relieved by ASME Code
approved practices (e.g., a full circumferential band of heat,
not localized on one side only).
wet

H~S

cracking and Hydrogen Blistering

Wet H2S cracking includes two distinct forms of cracking:


1)
2)

sulfide stress cracking, which affects hard welds on


carbon steel columns, vessels, exchangers, and piping;
and
SOHIC, (stress oriented hydrogen induced cracking), which
is a form of hydrogen blistering.

cracking and blistering are possible if steel is exposed to H2S


and liquid water, and typically occur when the water contains
more than 50 ppm dissolved H2S. Wet HaS cracking is caused by
the diffusion of hydrogen atoms into the steel as the material
corrodes. For more information on the wet H2S cracking
mechanism, refer to Section 300 of the Corrosion Prevention
. Manual.
For new vessels, use HIC-resistant steel and postweld heat treat
if the previous vessel had a history of cracking or blistering or
was located in a section of the plant with such a history. Limit
the hardness of the weld metal to 200 BHN maximum to further
reduce the risk of sulfide cracking. Before fabrication, inspect
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steel plate material using UT thickness gaging to detect large


laminations. After postweld heat treatment, inspect internal
welds with wet fluorescent magnetic particle testing. This
initial weld inspection will detect small fabrication defects,
which could later be mistaken for wet H2S cracks.
Because wet H2S cracking depends on the process environment,
certain pieces of equipment in an amine plant are much more
likely to crack than others. As part of the CUSA Refining Wet H2S
Technical Development Program, the CRTC Materials and Equipment
Unit collected wet H2S cracking data from Chevron refineries.
The 1993 survey data below indicate which pieces of equipment are
most susceptible to wet H2S cracking:
Equipment

% Cracked

Rich/Lean Amine Exchanger

H2S Absorber

between 40 and 60%

Amine Regenerator Reboiler

between 40 and 60%

Amine Regenerator OVhd. Condenser

between 40 and 60%

Rich Amine Flash Drum

between 20 and 40%

Amine Regenerator Reflux Drum

between 20 and 40%

NH3 Scrubber

between 20 and 40%

Acid Gas Knock-Out Drum

between 20 and 40%

Sour Gas Knock-Out Drum

< 20%

Amine Cooler

< 20%

60%

For details on these inspection results, contact the CRTC


Materials and Equipment Unit.
Hydrogen blisters can form i"n several areas of H2S removal
plants. Most blisters develop in the regenerator overhead
system. Cyanides in the overhead system from FCC offgas promote
blistering by destroying the protective iron sulfide film on the
steel surfaces . Blistering has also been detected in both the
upper and lower section of ammonia scrubbers, which are used in
amine plants in newer units. In very highly loaded MEA plants,
hydrogen blisters can form in the bottom of absorbers. Under
these conditions, blistering has been reported in the absence of
cyanide and ammonia.
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To control cyanides, ammonium polysulfide is sometimes injected


into the overhead system of the cracking unit (i.e. FCC or
hydrocracker) upstream of the amine plant. Most amine plants do
not use ammonium polysulfide injection, except as a temporary
measure. Typically, a plant would consider using polysulfide if
corrosion rates were high and a spot FeCl3 test detected
cyanides. (For details on the FeCl3 test procedure, consult CRTC
Materials and Equipment Engineering). The FeCl3 test is a
qualitative test for cyanides. The most reliable quantitative
test for cyanides is ion chromatography.
We generally recommend a nominal polysulfide injection rate of
five to ten times the stoichiometric amount needed to react with
cyanides in the process.
Polysulfide rates can be optimized by
monitoring hydrogen activity using hydrogen probes.
stress-corrosion crackinq of stainless steel Equipment

Austenitic stainless steels (300 series) are susceptible to two


types of stress-corrosion cracking in amine services: chloride
cracking and polythionic cracking.
Chloride Cracking

stainless steel tubes have chloride cracked in amine plant


regenerator reboilers, rich-lean exchangers, and MEA reclaimers.
Chlorides can be introduced with feed, produced water, make-up
water, or caustic soda or soda ash added to the reclaimer. To
reduce the risk of chloride cracking, make-up water should
contain less than 50 ppm chlorides. Note that process
requirements dictate a more stringent specification of 2 ppm.
(See section 3.8.)
Polythionic Cracking

Polythionic cracking is a form of intergranular stress corrosion


cracking, which affects sensitized stainless steels. Polythionic
acids have cracked stainless steels in H~S removal plants. For
further discussions of polythionic crack1ng, refer to section
3400 and section 300 of the Corrosion Prevention Manual. While
we would not expect polythionic cracking in CO2 removal plants,
sensitized stainless steels in these plants have cracked from
other forms of intergranular cracking
To minimize the risk of cracking of sensitized stainless steels,
we recommend the following practices for both H2S and CO2 removal
plants. Use only low carbon or stabilized stainless grades
(Types 304L, 316L, 321, or 347) where welding is required or for
u-tubes that require stress relief. Review stress relief
procedures to assure that they do not sensitize equipment. Use
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electric resistance stress relief methods for exchanger u-tubes.


Soda ash wash sensitized stainless steel equipment using a low
chloride soda ash, such as natural soda ash or a rayon or mercury
cell grade of caustic soda.
4.2

Influence of Design and operating Variables

Design and operating variables greatly influence corrosion in


acid gas removal plants. Changes in operating variables that
increase plant throughput tend to increase corrosion. This
section summarizes the influence of a number of these variables.
primary operating Variables
. Corrosion strongly depends on the following four operating
variables: temperature, heat stable salts, solution strength,
and acid gas loading. The effect of these variables is discussed
below.
Temperature
Corrosion is a strong function of temperature, with increasing
temperature increasing corrosion. The highest temperature and,
therefore, worst corrosion is usually found in the regenerator
bottoms system.
The high alkalinity of the amine minimizes corrosion until
reaching temperatures in excess of about 250F. Above 250F,
carbon steel corrosion is significant and special alloys and/or
inhibitors are required. This corrosion is probably related to
impurities and degradation products in the amine, such as heat
stable salts and other acid compounds.
In MEA reclaimers, tube metal temperatures above 300F - 325F
will degrade the amine and corrode the tube material, even if it
is stainless steel. Operating and design conditions must avoid
creating hot tube metal surfaces.
Heat Stable Salts
The total amine concentration in a solution is the sum of the
free amine and the amine tied up as heat stable salts. Organic
acids, sometimes formed in refinery processing plants or as a
result of oxygen. contamination, can cause serious heat stable
salt problems. Heat stable salts include oxalates, sulfates,
thiosulfates, acetates, formates, and thiocyanates. (For more
details see section 3.5.)

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Solution Strength
Another important factor affecting corrosion is amine solution
strength. Industry guidelines and company experience indicate
that the upper limit for MEA solution strength is about 20 wt.%
MEA in aqueous solution. Concentrations above this limit require
increased regeneration temperatures, which tend to degrade the
amine and increase corrosion. The upper limit for DEA solution
strength is somewhat higher (25 to 35 wt.%), while MDEA can be
used up to 50 wt.%.
Acid Gas Loading
A fourth primary operating variable is acid gas loading,
expressed as moles of acid gas per mole of amine. Acid gas
loading is related to acid gas feed rate and solution circulation
rates that are built into a plant design. Sizing a plant too
small or operating a plant above design limits will accelerate
corrosion.
The maximum acid gas loading varies depending on the type of
amine used. For MEA plants, acid gas (i.e. H2S and CO2 ) total
loadings above 0.4 moles acid gas per mole MEA cause significant
corrosion of .carbon steel equipment. If H,S levels are very low,
the steel is not protected well by a sulfiQe film, and corrosion
can occur above 0.3 moles acid gas per mole MEA. The limits for
H2S/DEA plants are somewhat higher at about 0.35 to 0.5 moles H2S
per mole DEA.
Control of amine solution strengths and acid gas loadings are
important corrosion control measures. Performing routine
chemical analyses is good operating practice. If plants must be
operated in excess of design capacity, it is better from a
corrosion viewpoint to operate with slightly higher solution
strengths and moderate loadings, rather than with normal solution
strength and high loadings.
Secondary operatinq Variables

From a corrosion standpoint, solution cleanliness and velocity


are secondary operating variables. They affect corrosion rates
in amine plants, but to a lesser extent than temperature, heat
stable salts, solution strength, or acid gas loading. However,
high solids content in the amine can lead to erosion and
corrosion problems.
Solution Cleanliness
contamination or degradation of amine solutions can lead to
serious corrosion and foaming problems. Contaminants can be
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oxygen, dissolved hydrocarbons, liquid hydrocarbons, and solids.


controlling solution contamination is necessary for long,
trouble-free solution life.
velocity/Turbulence

High flow velocities or turbulence can cause localized


erosion-corrosion in acid gas removal plants. For this reason,
piping design for carbon steel is limited to a maximum of 6 fps
fluid velocity. At turbulent areas in hot solution piping, long
radius bends (if possible) or stainless steel should be used.
Special care is needed at points of solution entry into vessels,
reboilers, and exchangers.
Erosion-corrosion and cavitation are common problems with pumps
in amine plants. Lean amine pumps and rich amine pressure
letdown valves often suffer severe erosion-corrosion. T-304
stainless steel, often hardfaced with Stellite, is usually
required to solve these problems. Pump' cavitation also leads to
accelerated corrosion. Calculation of NPSH requirements should
allow for the effect of dissolved gases, which is sometimes
overlooked. Installing the lean amine pump after the rich/lean
exchanger often solves this cavitation problem.
Longer piping and equipment lives can be obtained by selecting
the proper point to reduce the pressure of the amine solution.
Desorption of acid gases and dissolved hydrocarbons, which
usually occurs when the pressure of the rich solution is
significantly lowered, can corrode control valves and adjacent
downstream piping. The absorber or flash drum pressure should be
maintained through heat exchangers to minimize flashing of acid
gases.
4.3

Use of Alloy Bquipment

Equipment in amine plants is normally carbon steel (See Figure


4.1), with the exception of the applications discussed below. In
these cases, major refinery gas plants and selected producing
locations use stainless steel for high reliability.
Valves and pipinq

Alloys are used for two valve applications and several sections
of piping, which,are subject to erosion-corrosion. Stellite, hardfaced Type 304 stainless steel is used for' the absorber
bottom control valve and the pressure letdown valve to the
regenerator. Type 304L stainless steel is used for the following
sections of piping:

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Rich amine piping from absorber bottom control valve to


accumulator
Rich amine piping from pressure letdown valve to regenerator
Regenerator overhead reflux return piping
Hot lean piping from regenerator to rich/lean exchanger
Hot lean piping to reclaimer and return (MEA only)
Hot lean piping to reboiler and return
Lean Amine PUmp

This pump is usually T-304 stainless steel, but can be carbon


steel if potential cavitation problems are avoided. See Section
4.2 on velocity and turbulence effects.
Reqenerator

The regenerator is clad with T-304 stainless steel in two areas:


Above the feed tray where acidic corrosion is possible
Below the bottom tray where hot amine corrosion can occur
Excbanqers

T-304L stainless steel is typically used in three amine plant


exchangers: the rich/lean exchanger, the regenerator overhead
acid gas cooler, and the reboiler. In MEA plants, T-304L
stainless is also used for reclaimer tubes to provide resistance
to hot amine corrosion. Below are brief discussions on the use
of stainless steel in the first two services. Reboiler corrosion
is discussed separately.
The hot lean amine side of the rich/lean exchanger is generally
Type 304L stainless steel, althouqh some gas plants can use
carbon steel successfully. The cold rich side is carbon steel.
70-30 Cu-Ni has been used in H2S-free MEA/C02 plants where carbon
steel was not adequate. Plants using oxidative inhibitors (e.g.
Amine Guard) should use Type 304L, rather than 70-30 CU-Ni,
because oxidative inhibitors will pit the copper-nickel.
The tubes in the regenerator overhead acid gas cooler are usually
Type 304L stainless steel. If this' is an air-cooled eXChanger,
Type 304L is used for the inlet and outlet headers. Titanium
tubes are sometimes used in refinery H2S removal plants to resist
cyanide- and ammonia-induced corrosion. If titanium tubes are
used, we recommend grade 2 (commercially pure titanium) tubes
with the same material for the carcass and grade 2 or grade 12
for the tubesheet. Avoiding galvanic couples reduces the risk of
titanium hydriding.

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Reboi1er

Reboiler tube corrosion can be a serious operating problem in


acid gas removal plants. Corrosion is usually attributable to
high localized temperatures and to inadequate stripping in the
regenerator, which allows acid gas to be stripped in the
reboiler. Corrosion can occur under baffles when high pressure
steam (lS0 psi or greater) or hot synthesis gas is used for a
heating medium. Poor shellside flow in baffle crevices can
create high tube temperature zones, which increase corrosion of
stainless steel.
stress-relieved stainless steel reboiler tubes (Types 304L, 321)
are usually used in Chevron H2S and CO2 removal plants. Monel is
often used in MEA/COz plants when there are no sulfur compounds
present. In these plants, Monel has proved to be somewhat
superior to stainless steel in resisting high temperature
reboiler corrosion. However, Monel will pit if used in plants
with H2S or in plants using oxidative inhibitors, such as Amine
Guard.
Titanium shows promise in severe services where Monel and
stainless steel have had short (less than S year) service lives
because of corrosion. Company experience with titanium grade 2
reboiler tubes is limited to two reboilers in HS plants at
EI Segundo, in service since 1973 and 1975. Ti{anium reboiler
tubes have been known to hydride, and so require careful handling
during shutdowns. Hydriding does not affect tube corrosion
resistance.
Although often uneconomical in new plants where stainless steel
can be used, the design alternative to expensive tube materials
is to' lower the steam pressure in order to avoid high skin
temperatures and high heat flux rates. Low pressure steam at
so psi is usually recommended, with inlet temperatures monitored
to avoid superheat.
Mechanical design considerations, such as tube pattern and bundle
geometry, are important factors in reboiler corrosion. Refer to
section 3741 of the Corrosion Prevention Manual for discussions
on reboiler design.
4.4 Corrosion Inhibitors

For many years, both CO2 and H~S removal plants were inhibited
with organic, water-soluble f~lming amines (e.g. Kontol K-12 and
Betz WS-S8). Filming amines prevented sludge deposits, but their
success as inhibitors has been mixed. Betz WS-S8 is currently
used at the Carter Creek Gas Plant. The plant has over eight
years of experience with this inhibitor. To date, hydrogen
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blistering has not occurred while injecting WS-58 and coupon


corrosion rates have generally been less than 10 mpy. However,
at times, coupons in the rich stream through the rich/lean
exchangers have corroded at rates as high as 26 mpy.
DEA plants at Port Arthur and Richmond have had some success with
oxygen scavengers/metal passivators, such as Nalco 5173. Port
Arthur's 841 and 842 amine plants, along with the AVU 144 amine
plant (now out of service), have successfully used Nalco 5173 to
scavenge oxygen, which degraded the amine. A Richmond DEA plant
has used 5173 since 1990 to solve an iron sulfide fouling
problem. Although pump problems prevented continuous 5173
injection, the inhibitor appeared to stabilize the formation of
heat stable salts when it was injected consistently over a six
month period.
Adding the correct dosage continuously into a circulating solvent
or overhead system is critical to an inhibitor's success. If the
chemical is underfed, a passivating inhibitor can accelerate
corrosion. Underfeeding Nalco 5173 contributed to sulfide
cracking and corrosion problems at the carter Creek Gas Plant.
After injecting 5173 for about a year, severe cracking had
occurred in the bottom of the DEA regenerator. Additionally,
severe pitting was found in the hottest rich amine exchanger, and
steel coupons in a rich amine line had hydrogen blistered.
COz removal plants (usually MEA) sometimes employ oxidative
inhibitors, such as Union Carbide's Amine Guard. These
inhibitors contain metals (e.g. vanadium, arsenic, antimony),
which promote stable oxide films on carbon and stainless steel.
If H2S is present, oxidative inhibitors are not effective because
the formation of a sulfide film will compete with formation of
the oxide. Oxidative inhibitors tend to increase corrosion of
Monel and 70-30 Cu-Ni.
The use of oxidative inhibitors is declining due to restrictions
on their disposal. An alternative to inhibited MEA is MDEA,
which can be used at higher concentrations and does not require
inhibition. Oxidative inhibitors should not be used in MDEA
plants because they tend to increase corrosion.
4.5

Corrosion Xonitorinq

An inhibitor program will not be successful unless corrosion

rates in the system are continuously monitored. Both retractable


corrosion. coupons and corrosometer probes are used for this
purpose but coupons are preferred because field experience
indicates that retractable coupons give more reliable data under
both turbulent and laminar flow conditions. Also, coupons can be
visually examined for pitting. Corrosometers offer the advantage
CORROSION CONTROL

4.11

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

of continuous data collection, without the need for removing and


replacing coupons.
The location of probes or specimens should be chosen with care,
particularly if corrosion in the plant is highly localized. New
plants should have probe connections consisting of 1-1/2 inch
full port gate valves installed in critical locations such as
reboiler outlet vapor lines and the rich amine piping between the
rich/lean exchanger and the regenerator.
Probes may not be satisfactory if corrosion occurs primarily by
pitting or if the fluid velocities and turbulence at the test
location are sufficient to cause the probe element to fail by
fatigue. If the best test location is a highly turbulent area
such as the reboiler outlet line, better results will be obtained
with retractable corrosion specimens. Retractable specimens are
described in section 400 of the Corrosion Prevention Manual.
Coupons normally are removed at two-to-four-week intervals for
evaluation. Coupon data should be supplemented with inspection
data to confirm findings. Monitoring the solution's iron content
in CO2 plants, or the filter change frequency in H2S plants, can
also provide valuable information on relative corrosion rates.

CORROSION CONTROL

4.12

JULY 1994

Figure 4.1
Materials for Amine Gas Treating Plants

caRRaS ~ ON I

PIJR[F[EC
GAS

,f
AC:UMULnTORI

I
I

I
I
I

ABS.:lRSEil

,
I

n
-, I

SOUR
GIIS

,= n., T:Ri

I
7~04

', . ..

-' .0 (..... .;

t-:
/1. . ,..------..-----.

~
~

..

~
U ii :x~;~~~ O;c;,y [r Ii
~RESOtl.ER~~~~:
!'fO
1~~M~.o.21 I
m
TJ041..'
:
- n OKAY ,:- S~,
I.E.~N ~
~
:
MONEL OOE: Nor I
T

c:... " ..
....__
,.aiZ _____
.!
,

_;._w~

;.~5:

:i

.."ir
.. ...... "
i~
:~

~.

ff--- _["~::1

~~"~~=-.,

r,-::;

'_.,

Hor AM[NE CORROSiON. sec

I
I

"C;;:;K

_~ ~

, C I _Cl.l ~AX.
~ :GC ~PH CI-

i~
,t.
:~
i~Oql..
:~
:t..-_-.;:....._--..:11
" ....,;"')""',."",;;,;;,,)....),
NOTE!:

rl04L

!-!.2S

RICH-LEAH
EXCHANGER

C:C;~ERAl.

I
I

~~_*NHHNH',,2,,;,";;;;m'!!
~ Jh .....j '~!Si
i~

,1

'-c
= r-c"s

"

r=::i
rco t C::,LI. y
crt:::- - ~OE:-:
.--~"

- ALL CS xc~~r SHACEO AREAS


- Si-IAOEO a ALLOT. AS ~IOrE::J
- i~04/r304L HEAT ~~CHANC[RS iUBES. nuaE:HE:~:, BAF~:: IruaE!-~E~O~S :~ A!~ C:CL~~SI
iO AYOIO SENSiTiZAiiON. ONL'!' :<TRA-.. IJH C.~ftSON CE.:. :'~04LI OR ;;i.. aIL!Z:;iJ !:~AOES
IE.:. il2t. Tl471 OF ;;; SHOULO BE USiJ WME~E ~i~OtNC :R Si~ESS ~ELtE~ :s ~EaU!REu.
- VE~aC I n' ,.AX.: ; ~~'S PIP t Ne: ~ ~ FP'S ;;E" i ~:(CHAACC:"i
- SiRESS RE~tEr ITO AYOID AMINE 5C:1

_ . ' - " - ' . . . Mil.,


, - ALl.. PRESSURE VESSELS
...--.
- ALL PIPINC ;)lOO~ IEXcc:pr DE"/HOE,.cZ O.iJ.1

::.::.."!!!:--=--I:
-----...

...

I
II

I
I

Ii

Table 4.1
Amine Plant Inspection Guidelines

MEA

DEA.MDEA

WFMT3

WFMT

I every other scheduled shutdown


I every scheduled shutdown

(note 4)
1 every other scheduled
shutdown

1. Noostress-relieved Vessels 2

Inspection Method
Frequency
T less than ISOOf'
T greater than ISOOf'
2. Stress-relieved Regenerators
Inspection Method
FreQuency
3. Nonstress-relieved Piping'
Inspection Method
Frequency
T between 1(}()OF & 1500F
T greater Than 1500F

WFMT

WFMT
(note 5)

(note 5)

UT (S~ear Wave)

UT (shear wave)

50%15 years
50%15 years

(note 7)

50%15 years

NOTES:
1. Note some vessels otherwise exempt from me requirements for amine stress corrosion cracking inspection
may require special inspection for wet HlS cracking.
2.

Any evidence of or history of hydrogen blistering in a vessel necessitates iDspeaing all welds inrcmally,
using wet tluorescent magcetic particle teSting (WFMT).

3. WFMT = wet tluorescent magnetic particle testing.

4. From a technical viewpoint. the CRTC Materials and Equipment Unit does not consider it necessary to inspect
DEA and MDEA vessels operadDg at less than lSOCF. unless more than SO ppm HlS are present. In that case.

refer to inspection guidelines for wet H2S cracking.


S. If not done previously, schedule a one-time internal inspection of the boaom tbin1 of the regenerator column.
Any futme inspections will be determiIled by your findings.
6. Piping 1-1/2" and smallerneed not be inspeaed.

7. Inspection unnecessary unless stress cOII'Osion cracking has occurred elsewhere in the plant below

1500F.

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

5.0

MONITORING PLANT PERFORXANCE

The following recommendations were set-down by the Amine


monitoring sUb-team in conjunction with the Sulfur/Amine Best
Practices Committee after review and comment by Chevron
refineries, CRTC and amine suppliers.
5.1 Performance Goals
The purpose of this monitoring program is to provide the
information and guidelines necessary for maintaining a healthy
amine solution and for troubleshooting a poorly operating plant
so that the performance goals of the amine unit are met. These
overall performance goals in order of priority are:
MAKE ON-SPEC FUEL GAS & LPG.
prevent fuel-gas violations and near misses/alerts
due to excessive H2S)
MAKE CLEAN ACID GAS FOR RELIABLE SRU OPERATION.
prevent hydrocarbon and NH3 carryover.
prevent SRU/TGU violations and near misses.
OPERATE AT OPTIMAL CONDITIONS AND MINIMUM COST.
minimize utility and chemical costs.
maintain fuel gas and SRU feed quality.
RUN AMINE PLANTS WITH HIGH RELIABILITY.
minimize plant shutdown days, both planned and
unplanned.
5.2 Recommended Practice
1. It is recommended that sweet gas from individual absorber
columns be sampled one time each shift during normal operation
for H2S content. An alternative is continuous emission
monitoring (CEM). Some systems are simple enough that the fuel
gas system CEM can replace manual sampling. However, we cannot
recommend CEMs for each absorber outlet at this time. Data does
not support that the expense of a CEM will lower violations
Individual abs~rbers have their unique operating characteristics.
Regular sampling provides data required to optimize amine system
operation. and identify probable trouble spots in the gas treating
system. The test method is by individual location preference for
Draeger, Gas Tech, GC, etc.
Best Practice regarding sample apparatus and appropriate safety
MONITORING PLANT PERFORMANCE

5.1

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

precautions were developed by EI Segundo in June 1989. They are


attached.
2. It is recommended that overall fuel gas system H2S control
targets be established and location-specific reasons for said
target be documented.
All member locations operate the fuel gas sweetening systems to
meet permit limits. Most are about 160 ppmv H2S within some
averaging time period. Individual locations indicate target
limits from 25 ppmv up to 160 ppmv. It is not the intent of the
B.P. committee to specify actual targets for individual
locations. The practice of establishing targets based on
location specific requirements and experience leads to more
consistent and more economic operation of amine systems. It is
important that all crews know the control limit for each
absorber. Nothing is more frustrating than having an operation
changed from crew to crew.
3. It is recommended that unit specific recycle absorber
operating targets be established and specific reasons be
documented.
Recycle gas ~leanup may be set by process or refinery fuel gas
limitations. Most recycle systems are operated in a set-andforget mode. Actual operation should be monitored the same as
systems that produce sweet gas directly. A recycle bleed stream
that varies in H2S concentration contributes to instability in
downstream absorber operation. Over-operation of recycle
absorbers is not economic.
4. It is recommended that lean amine loading be analyzed once
per shift. Results should be reported in industry-standard units
of moles H2S per mole of free amine. Control ranges should also
be identified. An alternative (reduced) sampling schedule may be
justified if regenerator reboiler controls regenerator overhead
temperature.
Routine sampling of lean amine loading provides the background
data for troubleshooting system problems and optimizing
operation. Amine from the regenerator which is too lean
(overstripped) provides minimal additional cleanup capacity at
high cost. Change in lean loading may indicate instrumentation
problems on the. regenerator or possible contamination of the
amine (e.g. caustic).

MONITORING PLANT PERFORMANCE

5.2

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Typical Lean Amine Loadings for Normal Plant operation


Amine

Moles H2S/moie of amine


0.15
0.02
0.01

MEA

DEA
MDEA

5. It is recommended that amine circulation rate be monitored


both at the absorber and regenerator section of the individual
systems. This is a critical piece of information. Little
troubleshooting of performance problems can be done without this
data. System minimum and maximum rates should be identified and
documented. Maximum rates are set by absorber-tray flooding
limits. The minimum amine circulation rate is usually set by the
need to stay below maximum rich amine loading (see item 6).
Multiple meters provide cross-check ability. Discrepancies in
meters should be resolved in a timely manner. Minimum and
maximum rates need to be identified for individual absorbers and
regenerators.
6. It is recommended that rich amine loading be calculated on a
routine basis. Rich loading (as a rule of thumb) should not
exceed 0.5 moles of total acid gas (C02 + H2S) per mole of amine
in DEA and 0.35-0.40 for MEA. This maximum loading is
recommended to maximize the acid gas carrying capacity of the
amine while minimizing the acid gas flashing in the hot, rich
amine piping which would lead to excessive corrosion.
continuous on-line calculation of rich loading from amine and
sour gas flow is the easiest and safest method. For systems with
multiple absorbers, weekly sampling of H2S or C02 in sour gas
and sweet gas allows calculation of rich loading in each part of
the system. The most reliable method for monitoring rich loading
is direct measurement. Presently only one location routinely
samples rich amine. At this time the committee does not endorse
this practice. Eppendorf provides on-line analyzers (Carter
Creek uses this) that can accurately measure rich amine loadings
without the need for the safety concerns associated with richamine sampling. This may be justified in certain locations where
plant capacity and reliability are valuable.
The "best target" rich loading depends on the amine, amine
strength, velocities, temperature, approach to equilibrium (see
section 2.2) and plant design. This can be determined plant-byplant. Treating and materials experts or solvent suppliers can
assist with this. Carter Creek, for example, runs at .6-.7 mole
H2S/mole free amine.
7.

It is recommended that the lean amine temperature should be

MONITORING PLANT PERFORMANCE

5.3

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

at least 10F hotter than the sour gas to be treated. This


should be measured at the absorber. At several locations, long
distance of bare, lean amine piping cools the lean amine to a
temperature lower than the sour gas being treated.
This minimum temperature differential is a generally accepted
operating limit to avoid condensing light hydrocarbons into the
amine solution. At some locations, though, a higher differential
may be needed (i.e. 15-20F) if the rich amine flash drum
residence time is less than 15 minutes.
Amine temperature should be below 140F when treating process gas
for fuel gas use. As the lean amine temperature increases its
ability to make on-specification sweet gas will be impaired.
8. It is recommended that regenerator reboiler steam be adjusted
by TRC controlling the regenerator overhead gas temperature.
This proven method of maintaining lean amine quality (lOW lean
amine loadings) monitors the steam content of the regenerator
off-gas via temperature measurement. The amount of excess
(percentage) steam that exists in the regenerator overhead gas
can be measured by the regenerator overhead pressure and
temperature. This method of control maintains an optimal reflux
ratio for a desired lean amine loading with changing loads on the
regenerator. Attached (Figure 5.2.1) is a graph of Reflux Ratio
vs. Overhead Temperature at constant overhead pressure. Optimal
reflux ratios will depend on your units characteristics and
clean-up requirements. Starting points that have proven
effective for different amines are:
MEA

DEA
MDEA

Reflux Ratio
2.5
2.0
1.25

Moles H2S/mole free amine


.12
.02
.01

The Hawaiian refinery effectively controls their unit this way


with TDC-3000. This procedure for controlling regenerator steam
input circumvents the problems seen when acid gas loadings
change, circulation rate changes, and ambient temperatures
change. For this system to work effectively, you need good
regenerator pressure control (can't be swinging on SRU pressure)
and stable reflux temperature. If these are not stable,
controlling steam by ratio control to DEA circulation rate and
resetting that ratio based on overheadtemperature input will
work. An alternative to this control that is working at Carter
Creek is to tie steam control to on-line lean loading analysis.
A third and probably most common regenerator control method is
regenerator steam to amine circulation rate ratio control.
Typical ratios are 0.8-1.0 lb steam/gallon of amine circulation.
MONITORING PLANT PERFORMANCE

5.4

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

This method is effective if rich amine loading is relatively


constant. Under varying loads on the regenerator, though, the
first method is most effective.
Finally, in some locations, low pressure steam is essentially
"free" because it is being vented. In this case it may be
economic to overstrip the amine (high reflux ratios and very low
amine loadings) and recover the condensate. This will work if
the regenerator is not limited by flooding and the reboiler and
overhead condenser are not maxed out. Reboiler tube skin
temperature should be less than 350F (-120 psig saturated steam)
to prevent thermal degradation of your amine.
9. It is recommended that regenerator overhead water be tested
once per week for ammonium bisulfide content. Bleed rate should
be set to maintain a maximum of 10 weight percent.
The 10 percent limit is presently a corporate standard for sour
overhead systems. Failure to maintain this limit can cause
system corrosion and plugging. Excessive bleed increases sour
water production and associated cost.
10. It is recommended that total amine strength be analyzed one
time per day. CUSA Products recommended operating ranges with
upper limits for various amines are: MEA 15-20 wt%, DEA 25-30
wt%. and MDEA 45-50 wt%.
Regular monitoring of amine strength can be used to track system
losses. Maximum strength minimizes circulation requirements.
strengths in excess of the above limits are potentially
corrosive to the system. Also, at high concentrations, amine
losses increase because the solution lost by leaks, carryover,
and bleeds is more concentrated and the vaporization losses are
higher above more concentrated solutions.
statistical analysis of your data may warrant a less frequent
sample schedule if losses are low. However, when adding amine or
water to your system more frequent monitoring will be required.
11. It is recommended to keep the NH3 scrubber overhead
temperature below 120F. Above 120F there is NH3 carryover to
the SRUs and therefore plugging in the SRUs. NH3 carryover into
the amine acid gas stream will also cause ammonium bisulfide
. plugging in the, acid gas line.
12. The following is the recommended analysi,s of lean amine for
heat stable salt (HSS) and other contaminants.
Figure 5.2.2 summarizes the recommended monitoring program.
MONITORING PLANT PERFORMANCE

5.5

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Table 5.2.1:

Recommended Analyses

Test

Method

Reason

Li.it

Total Amine

titration

daily

plant specific

Maintain adequate solution


streangth and monitor losses

Free and Comined


Amine (total HSS)

CRTC
titration

weekly

trend should be < 10X


of total amine bcx.nd
by HSS

Control corrosion, insure


enough free amine for plant
performance, monitor losses

Iron

X-ray
Fluoresence

weekly

< 25 ppnw
trend should be stable
or declining

Indicates corrosion rate


trend.

weekly

desire clear, straw


colored amine.

Indicates corrosion,
contamination, degradation.

weekly

< 200 mg/l

Indicates loss of filter


effectiveness

desire low foam


stability

Indicates hydrocarbon, fine


sol ids in amine

Color and
Appearance
- Total Suspended
Sol ids TSS
Foaming, tendancy
and stabil ity

gas-sparged
test

weekly

HSS Anions

Ion
chromatograpy

quarterly

II

II

..
..

..

Formate
Acetate
Oxalate

Track individual ions to


better understand their
effect on corrosion; prevent
precipitation; determine
source.
< 2000 ppnw*

..

< 2000 ppnw*

II

II

< 3000 ppnw*

II

II

< 10,000 ppnw*

II

< 10,000 ppnw**

II

Thiocyanate

II

Thiosulfate

II

Sulfate

II

II

< 5000 ppnw**

II

Glycolate

II

II

II

Cyanate

..

N/A
N/A

II

Chlorides

X-ray
fluorescence

quarterly

< 500 ppnw

Indicates cooling water leak


or contaminated make-up
water. Danger of chloride
stress-corrosion cracking in
SSe

Sodiun

atomic
aborPtion

quarterly

< '_5wtX** (<8 wt%*)

Plugging and erosion

Calciun

atomic
absorption

quarterly

trend

Indicates cooling water leak


in c.w. condenser if present.

..

.*

Ash
quarterly
<10 wtX
ecommended
Llmlts r
by Dow Chemlcal Co., Gas/Spec Group, Jl.I'Ie 1993.
** Limits recommended by Union Carbide (Jim Ronnander), July 1992.

MONITORING PLANT PERFORMANCE

5.6

Plugging and erosion.

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

5.3

Sampling and Analysis

For guidance on gas sampling and sulfur analysis, refer to CRTC's


Guide to Analysis of Sulfur Compounds in Gases and Liquid (Feb.
1989). Other guidance can be obtained from the technical
memorandum by J. L. Creek of CPTC, Fluid Sampling. On-site
Analyses. and Calibration Procedures for Offshore California.
Although this was written for upstream natural-gas sampling, many
of its recommendations apply.
The use of flame photometric detectors (FPD) for GC analysis of
gas streams has been very successful at CRTC and other labs.
These detectors are very sensitive to sulfur compounds, although
the response is nonlinear. FPD's are applicable to the low
concentration range 1000 ppmv). A state-of-the-art detector,
used by the Fuels Group at CRTC and which has proved invaluable
for analyzing the myriad of sulfur species in Tengiz crude, is
the chemiluminescence detector. This instrument is sulfur
specific, very sensitive, and highly linear.
Sources of Analytical Assistance: The main contact at CRTC's
analytical group is Al Verstuyft (CTN 242-3403). He can answer
your general questions and route you to the proper expert.
CRTC's expert on amine analysis for total and free amine, HSS,
etc. by titrations and ion chromatography is Muigai Karigaca
(CTN 242-3701).
Assistance from sources outside of Chevron can be provided by
several laboratories:
Amine vendors (DOW, Union carbide, Huntsman, Coastal, Betz)
Core Labs
Western Research (SRU's)
Brimstone (SRU's)
5.4

Monitoring Trends

Once performance data (flows, temperatures, loadings,


concentrations, corrosion rates) are collected, they can be used
for optimizing and troubleshooting plant performance. Dow (Abry,
1993) recommends the use of control charts for analyzing plant
performance. Figures 5.4.1 and 5.4.2, taken from the Dow paper,
show examples of how control charts can be used to troubleshoot
inadequate performance. Figure 5.4.1 shows the relationship
between off-spec gas (the symptom), high lean loadings (the
intermediate), and low reflux ratio (the cause). The corrective
action would be to increase steam rate. Figure 5.4.2 shows
another case of off-spec gas, but in this case the lean loadings
are unchanged. The cause, foaming, is indicated by increasing
delta P in the absorber. The first action would be to give a
MONITORING PLANT PERFORMANCE

5.7

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

shot of antifoam to control the symptom. A search for the cause


of the foaming incident should immediately follow (look at lean
amine temperature, hydrocarbon interface levels in vessels,
etc.). The Dow paper provides an excellent troubleshooting guide
which in included as Tables 5.4.1 through 5.4.4.
Tables 5.4.5, 6 and 7 were prepared by CUSA Products. Table
5.4.5 presents a quick reference to the significance of the major
operating variables in an amine plant. Tables 5.4.6 and 5.4.7
indicate the methods used in routine analysis of untreated and
treated fuel gas streams in Chevron refineries and selected gas
plants.

MONITORING PLANT PERFORMANCE

5.8

JULY 1994

FIGURE 5.2.1

AMINE STRIPPER REFLUX RATIO CORRELATION


3
/

6PSIG

2.5

!i0:

-I
LL

0:
0.5

8-PSIG

"

10 PSIG

"
/

,. .-

/
/

"

.-

"

::J

/
/

12 PSIG

)(1.5

.-

,"

,,'

",

14 PSIG
16 PSIG

..

"
.... "
..

..,~

""

".

.- "
".

"

"

....

,. .-

,-

.-

,.

/
/

.-

""

....

,. /

'". ..

.-

... .-

"

".

".." ......

,,-".
.".- .....

.,~'

.,--

i~i~i~~.~.~ii~~;:~'~~ ::,::::'::,:='-'"

o170
~I~--------~~--------~::~---------L----------~------------~----------~
180

190

200

210

220

OVERHEAD TEMPERATURE ( F)
BAROMETRIC PRESSURE = 14.696 PSI
PRESSURES TAKEN AT STRIPPER OVERHEAD
Source: Dow Chemical Company by permission

230

____

-1

240

FIGURE 5.2.2
MONITOIUNG PROGRAM

SWEET GAS

II) NH3 scrubber overhead


temp Iimil = 120 max.

5) Circulation rate monitored 10 Absorber


& Regeneralor.
6) -Max. 0.5 molrlmole rich loading.
-On-line calculation of rich loading.
-Weekly check of individual absorbers

I) Sample lx/Shift or
CEM.
2) COritrollimil identifie
3) Recycle absorbers
limits sel by proceSs',

r-----_.."

ACID GAS

REGEN

OVIID

RICII DEA
SOUR WATER

A
8
S
7) -Lean amine 10 sour
gas delta T lOOP.
minimum.
-Aminetemp
<140o P.

S
T

I
P
P
E

R
B

9) Bleed 10 conlrol ammonium


bisulfide in overhead waler.
Sample IX/week. Max limit
10 wl% (Corp. slandard)

E
R

8) Reboiler conlrolled 10
maintain reOux ratio
by overhead temp
control.

SOUR GAS
L~AN

814191

DEA

4) Analyze loading lX/shift Target per


location requirements. Siandardize
reporting as moles H2S/moie DEA.
10) Amine strenglh analyzed IX/day 10
monitor losses. Maximum strength 10
minimize circulation. Limits: 20%
MEA, 30% DEA, 50% MDEA.

12) -Lean amine sampled


weekly for HSS by 10lal &
free DEA analysis.
-Quarterly delailed
analysis of amine.

FIGURE 5.4.1: Control Chart - Inadequate Stripping

6
/

5 .............. :.............. ;.............. .:...............~ .............. ~ ..../. ....... .

:
:
:
:
:/
:
:
:
:
i"
:
:
:
":
/;
.............. i ............ '';' ............ .; ..............:........ ,.-: .... ;. ...

0: 4
UJ

:
:
:

:
:
:

t-

. , .:
,:'

.
:

. .......

:.; :
..",..:
:.;
.

..
.
..
<:

....
.....
0:"

.
..
.. - .. - .. --:".... - .. -.............
.............. -:. ..............:.-............. .
<:2 .. - .. - .. -:.........
a.
:
.
.,.. .. --..
:
:
....... .. ~: ...... .......,
:
:
:

.
.
.
''--- .
1 .---.---.-:--.---.--~.--------t------~---.----~-.--
..
....
..
...

.
.
.
.

.
..
....
....

...
...
LU

.-.-.- ..;.-,.-.-.-~-.-.~.~:...............:.... . ........................

~3

~~~~~~~~~

--

II ' ' "I . '

10

15

20

25

ELAPSED TIME (Hours)


Outlet H2S
(ppm)
Lean Loading
(M/M * 1000)

- --

Lean Flow
Lean Temperature
(USGPM/100)
(Oeg F/100)

.----

Reflux Ratio
(Mole/Mole)
1_1._1'

1993 LAURANCE REID GAS CONDITIONING CONFERENCE


R.G.F. ABRY & M.S. DUPART. 93/03/01

(Used by Permission)

.........

..... .

:"':":..~ . .

30

FIGURE 5.4.2: Control Chart Foaming

6 ~----~--------------------------------~
5 .............. :.............. :.............. ":...............:- .............. :- ............. .

..
..
..
..

.
.
.
.
.

...
...
...
..................................................
CI: 4 .............................
.
.
., ... .
W

...
.
.
.
,

..
...
...
~

.
.
.

..
..
W
..
.-.-.-.~.-.-.-~-.-.-.-:.-.-.-.~.- .-.~.~...:.:. .....
~3

CI:
2
a..

'\

.:"

__

:
:

:
'
:
:

.:

____

.....
......;,.--~

,.~::

,.--.t -f... .. -

: ..
:
..
:
.... .:. .............. ............. .
",-'

",.,

.".

:
:

:
.:

.. .. .. _"._ .. .. .. .. .." ' - .:


.

.
.
.
.
.
1 ":':':':':'~:':':.!:~~:.!:'::':'~:':':':':4:'::,;,:,:,:,:,:,:,~:,;~:,:~:,:,:,:,:,::,;:,:,:!.:t:.:.:.::.:.~:.:.~~:.:.:.::.:.:.;
.....
,
.
.
.
.

..
..
..
..

...
.
...
...

..
o ~~~~'~~~-'~..~-'~~~-'--~~-'~~~~
o
5
10
15
20
25
30
ELAPSED TIME (Hours)
I

"',,,,,,,'

"

Outlet H25
(ppm)

Lean Temperature
Lean Flow
(USGPM/100)
(Deg F/100)

-----

Lean Loading Pressure Drop


(M/M * 1000)
(Psi)

.. --

'-"-1-

1993 LAURANCE REID GAS CONDITIONING CONFERENCE


R.G.F. ABRY & M.S. DUPART, 93/03/01

(Used by Permission)

.........

TABLE 5.4.1
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 100 high or 100 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 saipper pressure
Foaming in stripper
Contaminated solvent
Circulation rate below minimum tum 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 I plugged packing in absorber
No stages for removal
Poor disaibution I lack of contact between gas and amine
- Amine circulation rate 100 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 tum down
Poor hydraulics I loss of efficiency
- Maximum gas flow exceeded
Jet flooding I poor hydraulics I 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 I 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)
Source: Abry and DuPart, 1993 (by perT:1ission)

TABLE 5.4.2
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 filttation
- 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 5.4.3
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.
ENJRAINMENT LOSSES
GaslLiquid 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.
oRefer to Table 2.
Liquid/Liquid Applications Only:
o Unwanted or uncontrolled liquid in liquid dispersions (emulsions) formed.
oFluid velocity greater than 15 USGPM/ft2.
Packing material not steel or ceramic construction.
Amine superficial velocity> 60 ft/hr.
o Amine distributor orifice velocity> 170 ftlmin.
Damaged tower internals.
o Hydrocarbon superficial velocity> 130 ft/hr.
o H.C. disperser orifice velocity> 1.25 ftlsec.
0

SOLUBILITY LOSSES
Liquid/Liquid Applications Only:
o Amine concentrations greater than 40 wt%.
oLow system pressures.

o High system temperatures.


o MEA > DEA > MDEA.

V APQRlZATION LOSSES
Both Gas/Liquid & Liquid/Liquid Applications:
o High amine concentrations.
oLow system pressures.

o High system temperatures.


o MEA > DGA > DIPA > MDEA > DEA.

DEGRADATrON LOSSES
Both Gas/Liquid & Liquid/Liquid Applications:
Chemical degradation
o Reaction with carbon dioxide (MEA & DEA only).
o Reaction with oxygen (all amines).
Thermal decomposition
o Skin temperatures greater then 350 Deg F.
Hcat Stable Salt Formation
oInlet gas contaminants.
oOxygen degradation.
oThermal degradation byoproducts.

TABLE 5.4.4
TROUBLESHOOTING GUIDE FOR "CORROSION"

TYPES OF CORROSION
- General Corrosion
- Uniform material detecioration.
- 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.
- Intergranuiar 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 enaained gas bubbles.
- Saess 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 p~sence of, or the interaction of the metal with hydrogen.
SYMPTOMS
- High solution metals (Fe, Cr, Ni, etc.) content.
- Wall thinning using ulaasonic monitoring.
- Physical leaks.

- Vessel failure.
- High rates on coupons or probes.
- Positive solution corrosivity test.

PROCESS CONSIDERATIONS
- Rich acid gas loading too high due to low amine concenaations or undercirculation 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 saipping.
- 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 ~ron.
- Presence of heat stable salts will enhance corrosion.

TABLE 5.4.4 (Cont.)

TROUBLESHOOTING GUIDE FOR "CORROSION"

PROCESS CONSIDERATIONs (coot/d)


- Incorrect amine chosen for the intended use.
- Improper metallurgy in all or pan of the system.
- Solution flow velocities exceeding 3 fl/sec. in carbon steel and 8 fl/sec. in stainless steel.
- Large step changes, "either increases or decreases, in piping internal diameters.
- Shan radius elbows.
- Range 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 underdesigned, 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 temperawres exceeding 260 Deg F.

TABLE 5.4.5
Amine Treatine for H,S
- and CO,- R

Goal
Variable

H2S in
treated
product

"

Lean amine
loading

"

How does this variable


impact the goal?
Exceeding the
allowable H2S in the
product can result in
an emission violation.
H2S removal will

decrease if the
amount of acid gas
in the lean amine
gets too high.

"

Rich amine
loading

A high rich amine


loading minimizes
regenerator steam
consumption but can
cause severe corrosion
problems.

Heat stable
salts (HSS)
in amine
solution

"

High HSS content can


cause severe corrosion
problems.

Total amine
strength

"

High amine strength


minimizes amine
circulation rate and
operating cost but can
lead to increased
corrosion and amine
losses.

Importance

Why it's A, B or C

Who Monitors
Opr

How often monitored and


control range

"

Reliable, incident-free
operation is the primary
goal of an amine unit.

" "

Monitor once a shift.

"

Reliable, incident-free
operation is the primary
goal of an amine unit.

"

Monitor once a shift. Typical


lean loadings (mols H2S +
C02/mol free amine) are:
MEA 0.15; DEA 0.02;
MDEAO.01.

"

Rich amine loading is the


variable that determines the
trade-off between operating
cost (steam) and a high
operating factor. Most
plants put a higher priority
on reliability at the expense
of a higher operating cost.
Reliable, incident-free
operation is the primary
goal of an amine unit.

"

"

This is one of the key


variables that determines
the operability of an amine
unit.

Action

Engr

"

Calculate weekly by a plant


material balance. Typical
maxium rich loadings (mols

Increase amine circulation rate


and/or decrease the amine lean
loading if product exceeds the
allowable H2S specification.
Increase steam rate to
regenerator reboiler if lean
loading gets too high.

Increase amine circulation rate if


rich loading gets too high.

H2S + CO2 per mol free


amine) are:
MEA 0.35-0.40; DEA
0.50; MDEA 0.50.

" "

Monitor weekly. No more


than 10 wt% ofthe total
amine should be tied up as
HSS.

" "

Monitor daily.
Recommended
concentrations are:
MEA 15-20 wt%;
DEA 25-30wt%;
MDEA 45-50 wt%.

Caustic addition can reduce HSS


in the short term, but more than
1.5 wt% sodium in the amine can
cause plugging problems.
Ultimately HSS must be
removed, either by purging amine
from the system or preferably by
reclaiming the amine.
Reclaiming can be done either on
site or by sending the amine to a
reclaimer.
Adjust concentration by removing
amine solution from the plant and
making up with fresh amine or
water as required.

- - --._-

Goal
Variable

AT between

..j

2 3 .How does this variable


impact the goal?
Hydrocarbons can
condense out of sour
gas and cause
foamfng in amine
system if AT is too
low.

lean amine
and sour
gas

..j

Regenerator
reboiler
steam rate

NH4HS in
regenerator
overhead
water

..j

..j
Ammonia
scrubber
overhead
temperature

If overhead
temperature gets too
high, NH3 content of
the acid gas will
increase and cause
pluaaina in the SRU.

- . - - - - - -M

---

..j

..j

..j

..j

.... ,

Importance

Steam consumption
is a significant piece
of an amine unit's
operating cost.

Too high a
concentration of
NH4HS can cause
excessive corrosion
and plugging .

TABLE 5.4.5 (cont'd)


" .. -- .... .. _.
- .. Who Monitors

How often monitored and'


control range

Action

Why it's A, 8 or C

Opr

Foaming can upset the unit


and cause the treated
product to go off-spec.
Reliable, incident-free
operation is. the primary
goal of an amine unit..

..j

Check once a shift. Lean


amine should be at least
10F hotter than sour gas.

Control the AT by cutting back


on cooling water to the lean
amine cooler.

Operating cost in most


Chevron plants is less
important than plant
reliability.

..j

Check once a shift. Typical


steam rate is 0.8-1.0 Ib
steam/gallon of amine
.circulation.

Reliable, incident-free
operation is the primary
goal of an amine unit.

..j

Check once a week. Water


should contain less than 10
wt% NH4HS.

Most plants control by the Ib


steam/gallon amine ratio. If the
regenerator load swings, a better
method is controlling the steam
by the regenerator vapor line
temperature. Typical vapor line
temperatures at 10 psig for
different amines are:
MEA 225F, DEA 220F,
MDEA 210F .
Increase water bleed rate if
NH 4HS concentration gets too
high.

Reliable, incident-free
operation in both the amine
unit and SRU is the primary
goal of an amine unit.

..j

Monitor once a shift.


Overhead temperature
should be < 120F.

If temperature exceeds 120F


increase water makeup or
coolant rate.

Engr

TABLE 5.4.6
FUEL GAS SAMPLING - ONTREATED OR PARTIALLY TREATED STREAMS

REFINERY

SAMPLE
FREQUENCY

BREATHING
AIR

--

TYPICAL
CONTENT

Its

SAMPLE
METHOD

--

--

SAMPLE
PROCEDURE

--

COMMENTS

Not permitted to operate if amine


treating i. not effective.
Proces. plant. are shutdown.

EL SEGUNDO

Not Sampled

PER'I1I AMBOY

Each Shift

Yes

150-180 ppm

DrAeger TUba

Flow through .tream to


atmosphere at partially
treated ga. .ample chamber
with packing gland .nd
valve around DrAeger tuba.

Plan to upgrade to El Segundo


.ample .y.tem during Winter, 1991.

PORT AR'I1IOR

R.rely, one. or twice


y.ar

Yes

200-2000 ppm

DrAeger
TUba

I.olate .ample area. Route


mple .tream to
atmo.phere. In.ert DrAeger
tuba into flowing .tream.

Oparating Management concerned


about procedure.

PHILADELPHIA

Occa.ionally, when
amine tre.ting unit
down

Laboratory
TUtweUer

S.mple drawn in Tetlar bag,


analyzed at Laboratory.

u continuou. H2S

Ye.
to dr.w mple

Up to 2000 ppm

analyz.r for fual .ulfur contant


when SRU i hutdown. Alao,
notify all unit. via rigorou.
procedure when amina traater down.

RICHMOND

Rarely, la.. than


once/year

Ya.

>2000 ppm

Bomb or Bladder

Special procedure developed


if aver takan.

Taken a. .pacial tach .ervica


.ample only.

EL PASO

Each Shift
when SRU down

Ye.

>2000 ppm

DrAeger
TUba

Route .ample into bottle


and in.art DrAegar tuba to
analyza .ample.

Not .ati.fiad with thi. .y.tem,


intara.ted in what othar. do.

PASeJlGOULA

Twica/weak
RDS Unit only

Ya.

>1000 ppm

DrAegar
TUba

Routa .ample to bottle,


in.ert DrAager tuba to
analyza .ampla.

Intare.tad in what other. do.

Bomb, Lab
analy.i.

Flow through .amplar with


.amplar through bomb. Soma
vanting of ga. to
atmo.phare when
di.connacting bomb.

Analy.i. run at Lab. Oatanad


procedures for handling aample .

Weekly

GAVIOTA

Daily
only when amine
treatar ia .hutdown

HAWAII

CARTER CREEIt

DAR :jm.

Weekly

Ye.
with .tand-by
par.on

Up to
1000 ppm

No

Up to
2000 ppm

Itittagawa TUbe

Routa .ample .tream into a


bottle and ona insert tuba
into bottla.

Intars.tad in what other. do.

Ye.

>2000 ppm

Laboratory
Chromatograph

Flow through .ampla loop i.


connected to evacuated
bomb.

Vantil at ion hood and H,S alarma


utilizad in laboratory. wan

'/14/'4

developed procedure. in place.

Table'.doc

TABLE 5.4.7
FUEL GAS SAMPLING

REFINERY

SAMPLE
FREQUENCY

EL SEGUNDO

Each Shift

PORT AR'nIUR

BREATHING
AIR
No

No

Each Shift

TYPICAL
B 2 S CONTENT
5-20 ppm

5-20 ppm

TREATED FUEL GAS STREAMS

SAMPLE
METHOD
DrA.g.r Tube

DrA.g.r Tube

SAMPLE
PROCEDURE
Flow through .tream to relief
h.ad.r. Sample chamber with
rubber "packing gland" a.round
DrAeg.r tube. See attachment.
Opan .tream to atmo.ph.re; DrAeger
tube in.erted into flowing .tream.

COMMENTS

Recent redeaign is the beat

facility we have.

This addresses

environmental and safety cQncerns.

Operating Management concerned


about exposure.

Interested in

what others do.


PHILADELPHIA

Occa.ionally,
(DrAeg.r) to 3
time. par _.k
Lab

No

50-100 ppm

DrAeg.r Tube
and Trac.r
Analyz.r

Rout ampl. into a bottle and


in rt DrA.ger in bottle to
analyz . Obtain .ampl. in T.dlar
bag for lab analy.i. through
Tracor analyz.r.

Continuous H,S analyzer on fuel gas


.tr m. Sample only when H,S level
i. low to verify analyzer.
Int.re.ted in what others do.

RICHMOND

Each Shift

No

5-20 ppm

DrA.g.r Tube

Sampl.. are tak.n in a bladd.r at


low pre ure. Th. DrA.ger tube
fit. the bladd.r nozzle tightly.
Th. .ampl. i. drawn into the
DrA.ger tube for H,S content.

Continuous on-line analyzer. used


for H:zS measurement.
Will not

.ample if H,S level i. high.


Bladder samples takan occasionally
for hydrocarbon analysia.

EL PASO

Each Shift

No

5-10 ppm

DrAeg.r Tube

Rout ampl. into bottl., insert


Dra.g.r tube into bottle to
analyze .ampl .

Interested in what others do.

PASCAGOULA

Each Shift or
Each Day

No

5-20 ppm

Dra.g.r Tube

Rout ample into bottl., insert


Draeg.r tube into bottle to
analyze .ampl .

Interested in what others do.

Y , RDS

GAVIOTA

Weekly

No

5-10 ppm

Bomb

Flow through mpl.r with .ampl.


through bomb. Some venting of g.e
to .tmo.pher. to di.connect bomb.

Occaaionally, sample with DrAeger


tube. However, they have on-line
continuous analyzers for routine
reBulte.
Detailed sampling
procedures for bombs.

HAWAII

Daily to twice
par shift

No

5-20 ppm

BI.dd.r nd
!tittag.w. Tub.

Bl.dd.r r. an.lyz.d in a closed


mood. !tittag.w. tube. are u.ed by
in.erting into bottle which .lao
has .ampl. flowing into it.

On-stream analyzers exist on moat


stream sampled and analyzers are
routed to relief system.
Interested in what others do.

CARTER CREE!t

continuous
Analyzer

0-10 ppm

On-lin. g
chrom.tograph

Totally cont.in.d mpling system


with no r.l to atmo.ph.re.

On-line analyzers used at all

.-

timea. High H,S reading will shut


off gas flow to the plant, so they
cannot bypass amine treating.

DAR:jms

6/14/94

Table7.doc

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

6.0

ENVIRONMENTAL ISSUES

Environmental compliance is an essential component of the


operation of an amine unit or any other process. In refinery
fuel gas treating, the treated gas specifications are determined
by the air emissions permits for the facility. Amine units
create waste products, including used filter elements and liquid
wastes, that must be disposed of in accordance with waste
disposal regulations. This chapter describes the environmental
compliance issues for amine unit operation.
6.1

Refinery Fuel Gas Sulfur content

The amount of HzS that can be present in refinery fuel gas is


regulated. In the united States, the U. S. Environmental
Protection Agency has set a standard of 160 ppmv H2S in fuel gas.
Other state and local regulatory agencies have established
tighter standards. For example, the Richmond Refinery's fuel gas
specification of 80 ppmv is set by the regional Bay Area Air
Quality Management District. The H2S content of fuel gas must be
continuously measured and recorded with an online monitor. Some
regulatory agencies specify that a particular type of online
monitor be used.
At the preserit time, no regulatory agency in the united states
regulates the amounts of organic sulfur compounds such as
carbonyl sulfide and mercaptans that can be in refinery fuel gas.
This is likely to change in the future, however. The South Coast
Air Quality Management District in Southern California
established a maximum of040 ppm total sulfur in fuel gas, but
rescinded the regulation before it took effect. Removal of
organic sulfur compounds from refinery fuel gas requires a more
complicated treatment scheme than simple treatment with an amine
solution. A different type of online analyzer would have to be
used to monitor the sulfur content of the treated fuel gas. A
report on technologies for removing organic sulfur from fuel gas
was written by CRTC in 1992 and is available upon request.
In an amine unit with multiple absorbers, a fuel gas absorber
will determine the lean loading that is required in the stripper
bottoms. Fuel gas absorbers are operated extremely
conservatively: many produce treated gas containing 10-40 ppm
H2S. This provides a cushion in the event of a sudden increase
in the H2S content of the sour feed gas. It also provides time
for operators to respond to an upset before the fuel gas goes
off-specification. Process changes that may cause an increase in
H~S content of the treated gas include inadequate stripping of
the amine, an increase in the lean amine feed temperature, an
increase in the feed gas flow rate or acid gas content, or
foaming in the absorber.
ENVIRONMENTAL ISSUES

6.1

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

No refinery fuel gas absorber should ever produce treated gas


that fails to meet regulatory specifications. Unfortunately,
process upsets may lead to tne production of off-spec fuel gas
for short periods of time. Foaming upsets in the absorber are
the most likely cause of off-specification fuel gas. Operators
should be alert for early signs of foaming, such as a sudden
increase in pressure drop across the absorber or an unusually
variable pressure drop. A sudden drop in liquid level in the
bottoms compartment may also indicate foaming. At the first sign
of foaming, an anti-foaming agent should be injected into the
lean amine entering the column. The risk of foaming upsets is
minimized by good maintenance of the amine solution and
filtration of the feed gas to the absorber. However, an upset in
another refinery unit that sends a slug of liquid hydrocarbons
into the absorber will cause a foaming upset in the best
maintained units.
If an upset occurs that causes the treated fuel gas to exceed
regulatory specifications for HzS content for a brief period of
time, it is the responsibility of the permit holder to report the
violation to the proper regulatory agency. Regulatory agencies
will want to know how much ~S was burned above the regulatory
limit: this can be determinea from the records of the online H2S
analyzer...
.
6.2

Disposal of wastes from Amine units

All solid waste products from an amine unit, including used


filters and carbon, must be disposed of as hazardous waste.
Although it is possible to send amine solution to a refinery's
effluent treating system without violating permit conditions, it
usually is not a good idea. Amines act as fertilizer for the
microorganisms in a biological treatment pond, thereby increasing
the pond's biological oxygen demand by a substantial amount.
waste streams from reclaiming operations will contain heat stable
salts: these can be disposed of through an effluent treating
system. However, the soluble organic anions of the heat stable
salts will contribute to the toxicity of discharged water if they
are not biodegraded in biological treatment ponds.
spent filters can represent a significant disposal cost, since
they are usually sealed into drums and disposed of in a landfill.
cartridge filters do not fit efficiently into drums due to their
asymmetric shape. Some vendors sell "collapsable" cartridge
filters that can be pressed into a more compact shape before
disposal . The cost of disposing of cartridge filters is an
additional incentive to choose to install mechanical or bag-type
filters on any new amine unit. Bag filters are much smaller and
fill drums much more efficiently than cartridge filters.
Mechanical filters produce many fewer spent filters than other
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types of filters, since most particulates are separated from the


amine solution by gravity settling. sections 2.4 and 3.9
describe mechanical filters in more detail.

REFERENCES

6.1

Chevron Research and Technology Company report, "Treating


Options for Total Sulfur Reduction In Refinery Fuel Gas",
dated April, 1992

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70

ADD:ING CAPAC:ITY TO AN AM:INE UN:IT

Under certain circumstances, it may be desirable or necessary to


operate an amine unit above its design capacity for sour gas flow
rate or acid gas concentration. For example, a temporary
increase in throughput may be anticipated during a maintenance
shutdown of another amine unit. A permanent capacity increase
would be desired when an increase in the amount of sour gas that
requires processing or its acid gas content is expected to
increase.
This chapter has two objectives: to present a plan for executing
a capacity test of an amine unit, and to discuss alternatives for
debottlenecking one. The circumstances under which short-term
operation above normally accepted operating limits can be
tolerated are also discussed.
7.1

Determining the Capacity of an Amine unit

The capacity of every part of an amine unit except the absorber


is almost entirely a function of the circulation rate. The
capacity of the absorber depends on both the circulation rate and
the sour gas flow rate. Flooding calculations can be made for
the absorber .to determine whether its gas throughput capacity
will be reached before the plant's circulation rate limit is
reached. As a result, the capacity of an amine unit can be found
by determining the limit on its circulation rate.
A process simulation program can be very helpful for determining
the capacity of an amine unit. :In particular, a simUlation
program can show how the absorber will handle gases containing
different concentrations of acid gas. They can show what the
temperature profile in the absorber will be, and what circulation
rate will be required to maintain an acceptable rich loading.
This may be the only way to predict whether an absorber can
process feed containing higher levels of acid gas, since it may
not be possible to change the composition of the sour gas feed to
an amine unit in order to conduct a capacity test. Process
simUlation of amine units will be discussed in more detail in the
next chapter.
7.1.1

Planning and Executing a capacity Test

The first step .in planning a capacity test is to schedule it with


Operations. All areas that will be affected by the capacity test
should be. aware of the test and agree on the timing. The
facility's analytical laboratory should agree on the date as well
and be prepared to perform analyses of the lean amine and gas
entering and exiting the absorber. If these analyses cannot be
performed onsite, plans should be made to send samples to an
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outside laboratory.
The second step is to gather in advance all of the materials that
will be required for the test. Design drawings for all of the
equipment and piping in the unit should be collected and checked
to see that they are up to date. These drawings will provide the
information that is required to analyze the results of the
capacity test. An adequate supply of sample containers should be
available.
The third step is to have all of the important instruments in the
unit calibrated. All flow meters and pressure indicators should
be checked. Enough thermocouples should be checked to provide
the temperatures of fluids leaving each heat exchanger and the
top of the stripper column.
When the test is started, the plant's circulation rate should be
increased in increments of no more than 10%. If the unit is
believed to be operating near its maximum capacity, increments of
no more than 5% should be used. The amine unit may take 45
minutes or longer to reach steady-state operation again, since
the entire solvent inventory must circulate through the unit
under the new conditions. The plant's operators should make
adjustments to coolers and the stripper reboiler in order to
maintain the "desired set points. Once the unit has reached a new
steady state, samples of the sour gas, treated gas, and lean
amine should be taken for analysis. The circulation rate can
then be increased again and the procedure repeated.
When the unit's maximum circulation rate is reached, operators
will not be able to adjust some operating variable enough to
bring the unit back to some desired setpoint. The types of
limits that are encountered in amine units are discussed in the
next section.
7.1.2

Factors that Limit capacity in Amine units

The limit on circulation rate in an amine unit will likely be due


to one of the following factors:
Downcomer flooding on trays in the absorber or stripper
and amine carryover.

Inadequa~e

heat transfer in the lean/rich exchanger.

Inadequate cooling in the lean solvent cooler or stripper


condenser.
Inadequate reboiler duty/not enough boilup.
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Pump capacity limit or insufficient NPSH.


The lean/rich exchanger will not limit the unit's capacity by
itself. However, the loads on both the stripper reboiler and the
lean amine cooler will increase if the lean/rich exchanger cannot
achieve the design temperature approaches.
The easiest capacity limit to determine is a pump limit. If the
circulation pumps (or the booster pumps, if present) are
operating at their circulation limit, operators will not be able
to increase the circulation rate. A limit might also be reached
if the increased flow rate causes too much pressure drop in the
piping leading to the pumps, creating a shortage of NPSH. In
order to check whether this is the case, field operators should
monitor suction pressure and also listen for sounds of cavitation
in the pumps after each circulation rate increase.
An increase in the lean amine loading indicates that the stripper

reboiler cannot provide enough heat to regenerate the amine


solution. This may be due to a capacity limit on the reboiler
itself or a combination of inadequate performance of the
lean/rich exchanger and the reboiler. If the temperature
approach in the lean/rich heat exchanger is higher than normal,
the exchanger is not heating the rich amine to the expected
temperature hefore entering the stripper. When this occurs, the
reboiler must provide more duty for sensible heating. This will
cause the reboiler to reach a capacity limit before it would
otherwise.
Amine reboilers should not be operated with heat fluxes greater
than 6,000 Btu/hr-ft2 - OF when hot oil is the heat medium, or
6,000-8,000 Btu/hr-ft2 - OF when steam is the heat medium. Fluxes
greater than these can lead to rapid corrosion of the reboiler
tubes due to film boiling of the amine solution. If the maximum
heat flux is reached, the reboiler should be considered to be
operating at its limit.
Flooding may occur in the stripping column due to excessive
liquid and/or vapor traffic. Flooding is characterized by an
abnormally high and variable pressure drop, carryover of amine to
the reflux drum, and an increase in the lean amine loading due to
reduced column efficiency. In most instances, the stripper will
flood due to inadequate volume in the downcomer for allowing
entrained gas t9 disengage from the solution. This causes froth
to build up on the tray, which in turn causesa large amount of
entrained. amine to be carried to the tray above.
The stripper overhead condenser may also prove to limit the
capacity of the amine unit. When the condenser is operated
beyond its limit, the temperature of the acid gas will be higher
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than normal. Because of the higher temperature, more water will


be carried out of the unit by the acid gas. This will increase
the make-up water requirement. In addition, water may condense
in the line to the SRU. If the SRU does not have a knockout
drum, or if it is difficult to remove liquid from the knockout
drum, this will not be an acceptable mode of operation. This is
why amine units are rarely operated above their condenser limits.
The circulation rates at which the stripper, reboiler, and
condenser reach their capacity limits depend on the reflux ratio
of the column. If the reflux ratio is higher than necessary,
simply lowering the reflux ratio will increase the capacity of
the unit if one of these pieces of equipment is limiting the
unit. Section 5.2 gives guidelines for reflux ratios in amine
strippers.
The temperature of the lean amine entering the absorber may rise
to an unacceptable level due to a capacity limit in the lean
solvent cooler. The load on the lean solvent cooler will
increase if the lean/rich exchanger cannot cool the solution down
to the design temperature due to a capacity limit. Feeding
warmer amine to the absorber will result in higher HaS and CO2
levels in the treated gas. Most amine units are des1gned to cool
the lean amine to lOO-120 0 F. Depending on the service, however,
it may be possible to use a lean amine feed temperature up to
140 0 Fand still meet treated gas .specifications. Before feeding
warmer amine to the absorber, however, it would be prudent to
verify that the unit will still meet the treated gas
specifications by process simulation or some other method.
Flooding in the absorber may occur at higher gas flow rates or
increased acid gas concentrations and the higher circulation
rates required for the new conditions. However, it is unlikely
that either an increased flow rate or a higher acid gas
concentration in the feed gas can be provided for the purposes of
the capacity test. As a result, flooding calculations for the
absorber will need to be made separately from the test.

As the circulation rate is increased during the test, downcomer


flooding may occur even without increasing the gas flow rate.
Downcomer flooding occurs when there is not enough volume in the
downcomer to allow entrained gas to disengage from the amine
solution. This causes amine froth to back up onto the tray,
which in turn causes a large amount of entrained amine to be
carried to the tray above. When this occurs, the column floods.
Flooding in the absorber is characterized by an abnormally high
and variable pressure drop, carryover of amine solution from the
absorber, and an increase in the H2S and CO2 content of the
treated gas. If downcomer flooding occurs, it is a certainty
that the absorber will not be able to handle a higher gas flow
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rate because increasing the gas rate will make downcomer flooding
occur at an even lower circulation rate.
If the amount of acid gas fed to the absorber is increased and
the circulation rate is not increased, the rich amine loading
will increase. since rich loadings are kept at or below certain
levels (see Table 3.1.1) in order to prevent corrosion, this will
establish the limit on the amount of acid gas that the unit can
handle. However, if the absorber does not flood under such
operating conditions, increasing the rich loading above normal
levels can allow the plant to treat higher gas flow rates or acid
gas concentrations for a brief period of time.
7.2

Temporary operation at Elevated Rich Amine Loadings

In some instances, increased capacity in an amine unit will be


needed for a period of a few days or weeks. Such a situation
might occur when an amine unit is shut down and other units in
the facility need to be operated at higher capacity to treat the
gas normally treated by the shut-down unit. In such a situation,
it may be desirable to operate the unit at higher rich loadings
than normal. This may involve operating the unit at rich
loadings higher than commonly accepted guidelines would allow.
Typical guidelines for maximum rich amine loadings in H2S removal
applications are 0.5 moles of acid gas per mole of amine for DEA
and MDEA and 0.4 mol/mol for MEA. Operation within these limits
will almost always ensure that general corrosion rates in plants
built entirely of carbon steel will be less than the commonly
accepted limit of 0.005 inches per year (5 mpy). In plants that
have stainless steel in corrosion-prone areas, general corrosion
rates will usually be less than 5 mpy when these rich amine
loadings are used. Operation at higher loadings will lead to
higher corrosion rates, with the corrosion rate increasing more
than linearly with the increase in loading. A more thorough
discussion of corrosion in amine units can be found in Chapter 4.
Although operation at higher rich loadings will increase the
corrosion rate significantly, a carefully maintained amine unit
can be operated in this manner for a brief period of time.
Operation of an amine unit at rich loadings more than 50% greater
than the recommended maximum for any period of time is not
recommended. While the unit is being run at elevated loadings,
corrosion coupo~s should be checked no less than twice per week.
If a level of corrosion is seen that is considered to be
unacceptable, the loading should be reduced immediately.
Any decision to operate at elevated rich loadings should be made
only after a careful evaluation of the unit and the expected
corrosion rates. This decision should be made by responsible
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

Operations personnel working in consultation with corrosion


specialists. The Management of Change process should be used
when deciding whether to proceed. Some effort should be expended
to determine a baseline level of general corrosion rates in the
unit under the current operating conditions. If the corrosion
rates are already significantly higher than 5 mpy, it would not
be wise to increase the rich loading. The amine should contain
low levels of heat stable salts and entrained particulates, since
thesecontaminants contribute to the corrosivity of the amine
solution.
Since there is no precise way to predict what corrosion rates
will be for a given rich loading in any particular unit, testing
is the only way to determine this. Based on the information
gained from the test, Operations can decide whether to operate at
elevated rich loadings, and, if so, what level of accelerated
corrosion they are willing to accept for a brief period.
Operation at elevated rich loadings for an extended period of
time will shorten the life of the plant because of general
corrosion rates that exceed the design values. When deciding
whether to operate in this manner, it is essential to remember
that this is just a way to gain extra gas treating capacity for a
short period .of time. If a permanent increase in capacity is
needed, the unit must be debottlenecked by modifying or replacing
whatever components are limiting its capacity.
7.3

DebottleDeckiDq an AmiDe UDit

Pumps

The ease with which an amine unit can be debottlenecked depends


on what the source of the capacity limit is. If a pump proves to
be the bottleneck, it may be possible to install a larger
impeller or replace the pump at a relatively small cost. If a
pump is limited by NPSH, it may be possible to replace the
suction piping with larger diameter pipe to reduce pressure drop
and increase the available NPSH. Increasing the capacity of
other pieces of equipment will be more expensive.
Absorbers

If the absorber is limiting the capacity of the unit, several


approaches can b.e used to debottleneck it. Single-pass trays can
be replaced with two-pass trays, or two-pass trays can be
replaced with four-pass trays. Trays with more passes can be
designed for larger downcomer volumes for a given column
diameter. This will increase the capacity of the absorber,
especially if the downcomer capacity is limiting the tray
loading. Increasing the number of tray passes will decrease the
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

tray free area slightly, however, so each tray will reach its
vapor rate limit sooner than it would otherwise. Increasing the
number of tray passes will not add capacity to a vapor rate
limited absorber because of this. This type of retrofit is most
appropriate for cases where the acid gas content of the feed gas
is expected to increase, since additional liquid circulation is
required for treating roughly the same amount of gas.
Replacing the trays in the absorber with packing will add even
more extra capacity than switching to multipass trays would.
When compared to trayed absorbers, packed columns have a higher
percentage of their cross-sectional area available for contacting
the gas and liquid because the downcomer area is eliminated.
Since amine absorbers have unusually large downcomers, switching
to packing will add substantial extra capacity to the column.
Packed absorbers have roughly 30% more capacity for both gas and
liquid than trayed contactors with the same diameter.
However, switching from trays to packing results in a lower
number of theoretical stages in the absorber. In an absorber
with 20 trays on a 2' spacing, there are 38' for the contacting
section. This is enough room to install three 10' packed
sections with redistributors below the top two sections. In
amine services, the HETP for 2" random packings is between 8' and
10'. As a result, the packed absorber will have between three
and four theoretical stages. In ~S removal applications,
absorbers with 20 trays usually have between four and five
theoretical stages. Of course, fewer theoretical stages result
in less acid gas removal. Depending on the specific application,
it may be possible to operate with fewer theoretical stages and
still meet the treated gas specifications. There are two reasons
for this. First, although virtually all absorbers are designed
with 20 trays because basic design guidelines call for this
number, fewer trays could be used in many applications. In
addition, most of the acid gas is removed in the bottom two
stages in most absorbers. As a result, the increase in acid gas
content of the treated gas may be acceptably small if a
theoretical stage is removed. Before any decision is reached to
switch from trays to packing, the performance of the packed
absorber should be modeled using process simUlation or
equilibrium data.
."

If the absorber is limited by circulation rate (downcomer


flooding), a "precontactor" can be added in front of it. A
precontactor is a device for contacting amine and sour gas before
the absorber. Typically, one would consist of a spray nozzle,
inline mixer, and a separator vessel. A separator vessel is
usually required because there is normally not enough room in the
bottom of the absorber between the inlet nozzle and the bottom
tray to allow the amine solution to fully disengage from the gas.
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Depending on the type of inline mixer used, up to one theoretical


stage of contact can be provided. A precontactor will remove a
significant percentage of the acid gas in the feed, thereby
reducing the amount of amine that needs to be fed to the
absorber. This will increase the unit's gas handling capacity by
a substantial amount.
Amine fed to a precontactor will approach its equilibrium loading
with the sour gas. If the acid gas content of the sour gas is
high, this may lead to rather high rich loadings and elevated
temperatures due to the heat of reaction between the acid gases
and the amine. In order to prevent excessive corrosion,
stainless steel may be required for the inline mixer, piping
between the mixer and separator, and the rich amine piping
returning to the rich amine flash drum. Corrosion protection may
also be necessary in the separator vessel. If the temperature of
the gas leaving the separator is greater than 140 0 F, a gas cooler
may be required to cool the gas before it enters the absorber.
Adding a precontactor involves several new pieces of equipment
and runs of piping. When compared to retraying or switching from
trays to packing, it is an expensive option. It is inexpensive
only when compared to purchasing a new absorber.
A packed absorber handling liquid LPG can be effectively
debottlenecked by replacing random packing with structured
packing. Compared with conventional packing such as Pall Rings
or Cascade Mini-Rings, Koch's Sulzer SMV structured packing will
allow a 50-100% increase in capacity, as well as provide a more
efficient packing. Richmond Refinery is installing structured
packing to debottleneck liquid propane absorber.
Amine stripping Column

Two of the methods that can be used to. add capacity to an


absorber can also be used in a stripping column: switching to
trays with more passes or by switching from trays to packing.
switching to trays with more passes can increase the downcomer
area: this will increase the column's capacity for liquid traffic
but not its capacity for vapor traffic. Since the vapor and
liquid rates are always directly proportional to each other in a
stripping column, this will not be an effective way to add
capacity unless the trays have excess capacity for vapor traffic
.' before the change is made.
switching. from trays to packing adds up to 30% extra capacity for
both vapor and liquid traffic. However, the column will have
fewer theoretical stages of contact. This may require that the
column be operated at a higher reflux ratio in order to maintain
the desired degree of stripping. In addition to increasing the
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

operating cost of the unit, the additional steam and refluxing


water will use some of the additional capacity provided by the
packing. Before deciding to change from trays to packing, the
performance of the unit should be evaluated using process
simulation, equilibrium data, or field data from a similar
facility that has been retrofitted with packing.
Beat Exchangers
If a heat exchanger is limiting the capacity of the unit, it is
likely that an additional exchanger will have to be installed in
order to provide additional capacity. For a water-cooled
stripper condenser or lean amine cooler, however, it may be
possible to obtain additional cooling by increasing the cooling
water circulation rate through the exchanger. If the exchanger
itself is not limiting the water circulation, and incr.ease in
flow might be obtained at relatively low cost by replacing the
cooling water piping with a larger line.
If the reboiler is limiting the unit, it will be very difficult
to debottleneck it. It may be possible to replace the existing
reboiler with a larger exchanger. This may not always be
possible due to the layout of the plant. If the reboiler is a
thermosyphon, the circulation rate that can be provided through
it may be limited by the geometry of the bottom section of the
stripping column. Adding a second reboiler for operation in
parallel with the existing one is possible. Since it is
essential to have exactly the same pressure drops in the piping
to and from the column as exist in the first reboiler, the second
reboiler will have to be located close to the column. Depending
on the layout of the plant, this may not be possible.
If the capacity of the reboiler is limited by the amount of heat
medium that can be fed to it, some capacity can be added by
replacing the heat medium pipe runs to and from the reboiler with
larger pipe. Before deciding to replace these pipes, however,
the heat flux in the reboiler should be calculated. It is
im~ortant to keep the flux in the reboiler below 6,000 Btu/hrft _OF when hot oil is the heat medium, and below 6,000-8,000
Btu/hr-ft2 - OF when steam is the heat medium. Fluxes greater than
these can lead to rapid corrosion of the reboiler tubes due to
film boiling of the amine solution
7.4

switching from DEA or IlEA to KDEA

switching. from MEA or DEA to MDEA is one way to increase the


capacity of virtually any amine unit. As discussed in Chapter 3,
MDEA is a tertiary amine. This makes MDEA less basic than either
DEA or MEA. As a result, higher solution strengths of MDEA can
be used without experiencing corrosion problems. MDEA is
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

frequently used at strengths up to SO%. These higher solution


strengths more than offset MDEA's higher molecular weight. with
rich loadings of O.S mol/mol in each solvent, a 50% MDEA solution
can absorb over 40% more acid gas per gallon of solvent than a
30% DEA solution. In addition, MDEA has selectivity for H2S over
CO2 If substantial amounts of CO2 are present in the gas and
complete CO2 removal is not required, a reduction in amine
circulation requirements will result from allowing some COz to
"slip" through the absorber. Since MDEA is a weaker base than
either DEA or MEA, the reboiler duty will not increase; in fact,
it may decrease somewhat. These factors allow a circulation
rate-limited amine unit to remove more acid gas using MDEA than
using DEA or MEA. MDEA can be used in LPG treaters that are
currently using DEA or MEA without any equipment modifications.
Although MDEA is available as a generic product, it is often
purchased in the form of a proprietary amine product.
Proprietary MDEA-based solvents can be either straight MDEA or
blends of MDEA with other materials. The blends can offer either
enhanced selectivity for H2S over CO2 or enhanced kinetics for
bulk CO absorption. Some common trade names for families of
proprieEary MDEA-based solvents are Dow Chemical's Gas/Spec
solvents and Union Carbide's Ucarsol solvents. Dow's Gas/Spec
SS-1 and Union Carbide's Ucarsol HS-101 are both straight MDEA.
When deciding whether to switch from MEA or DEA to MDEA, the
following factors should be considered:
MDEA is a more expensive solvent than MEA or DEA. Generic
MDEA costs $1.1S/lb, whereas DEA costs roughly $0.60/lb.
Proprietary solvents cost more: the proprietary solvents
that are plain MDEA cost around $1.2S/lb.
MDEA solutions are more viscous than DEA or MEA solutions.
This will produce higher pressure drops in piping,
possibly resulting in inadequate NPSH for a pump, change
the performance of pumps, and produce less efficient
heat exchange. In most cases, heat exchangers do not have
to be modified when switching to MDEA. However,
circulation pumps or their suction piping may have to be
replaced.
It is more difficult to design an MDEA unit than it is to design
a DEA or MEA unit, especially if the application involves
selective HzS removal. CRTC is unaware of any process simUlation
program that has adequate equilibrium data to accurately model an
MDEA absorber or stripper. In addition to equilibrium data, some
sort of kinetic model is required to predict CO2 absorption into
MDEA. CRTC recommends that anyone who wishes to use MDEA
purchase a proprietary MDEA solvent even if generic MDEA will do
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AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

the job. Choosing to use a proprietary MDEA solvent rather than


generic MDEA is a prudent decision because solvent vendors will
provide an accurate heat and material balance that can be used
for the design. Anyone who wishes to design an MDEA unit
themselves should rely on published equilibrium data for H2S
removal and stripping, and published kinetic models for CO~
absorption. This literature can be obtained from CRTC's L1ght
Hydrocarbon Processing Team upon request. Even with this
information, however, designs cannot be made in-house for blends
of MDEA with other amines or MDEA solvents that contain compounds
that catalyze CO2 absorption.
Amine units using MDEA must be maintained more rigorously than
units using other amines. MDEA losses must be kept to a minimum
due to the solvent's high cost. The higher solution strength
solvent has a lower surface tension and is more prone to foaming
upsets than other amines. As a result, it is essential that the
solvent be filtered for particulate removal constantly and
effectively. Many units using MDEA are equipped with filters for
100% of the circulation. Although MDEA does not degrade as
rapidly as other amines, the corrosive effects of heat stable
salts are even more pronounced in MDEA due to its higher solution
strength. The solution must be treated regularly for heat stable
salt removal. In applications where heat stable salt buildup
occurs rapidly, an online reclaiming system would be a wise
addition to an MDEA unit (see section 3.10).
REFERENCES

7.1

Astarita, G., D. W. Savage and A. Bisio, Gas Treating with


Chemical Solvents, John Wiley and Sons, 1983.

7.2

Kohl, A. L., and F. C. Riesenfeld, Gas Purification, Gulf


Publishing Company, 1985.

7.3

Gas Processors' Supply Association, Engineering Data Book,


Volume 2, Chapter 21.

7".4

Lieberman, N. P., Troubleshooting Natural Gas Processing:


Wellhead to Transmission, Chapter 12.

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8.0

PROCESS SIMULATION

8.1

Introduction

Process simulators are a useful tools for troubleshooting amine


units, optimizing their operation, and predicting the effects of
changes in feed or operating conditions on their performance.
Since amine units contain the same types of unit operations that
are common in other production and refining processes, simulating
them is similar to simulating other processes.
There is, however, an unusual feature of amine units that makes
creating a simulation program that will give satisfactory results
a challenge for simulation program vendors. Most other
absorption and stripping operations are based on physical
solubilities of gaseous compounds in the solvent. In amine
units, however, chemical reactions between the acid gases and the
amine take place during absorption and stripping. As a result,
the amount of acid gas absorbed or desorbed often depends more on
the mass transfer rates and length of time that the liquid and
gas are in contact with each other than on the equilibrium
distribution of H2S and CO~ between the two phases. This is
particularly true in sect10ns of the absorber and stripper where
large amounts of absorption or desorption take place.
The theoretically correct approach to simulating amine absorbers
and strippers would be to model the heat and mass transfer
processes that take place on each tray (or section of packing).
Using this approach, the equilibrium calculation predicts the
driving force for mass transfer rather than the performance of
the tray. Unfortunately, the one commercially available
simUlation program that uses this approach, Aspen Technologies'
. Ratefrac, has a poor data package for amines and gives poor
results. Other simulators rely on equilibrium stage models for
the absorber and stripper.
There are two simUlation programs currently available that give
accurate results for amine unit simUlations: TSWEET by Bryan
Research and Engineering and AMSIM by D. B. Robinson and
Associates. AMSIM is available as a stand-alone program or, more
conveniently, by selecting the "amines" property package of
Hyprotech's HYSIM process simulator. Both TSWEET and AMSIM
perform quite well for systems using MEA or DEA. A 1991 CRTC
study (reference 9.3) which compared TSWEET and AMSIM simUlations
to plant data from several sites found TSWEET to be slightly more
accurate . TSWEET is considerably easier to use than AMSIM, so it
would be preferred for most applications if both are available.
No currently available simulator gives trustworthy predictions
for selective H2S removal applications using MDEA. The
PROCESS SIMULATION

8.1

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

selectivity of MDEA is not determined by equilibrium


concentrations of HzS and COz' but rather by different rates of
absorption of the two compounds. The more slowly absorbed COz
may never approach equilibrium with the MDEA solution in an
absorber. As a result, the selectivity cannot be predicted well
by any equilibrium stage model. simulations using TSWEET and
AMSIM (or HYSIM) can be matched to a set of operating data for an
MDEA unit by adjusting certain parameters (the residence time in
TSWEET and the tray efficiencies in AMSIM). However,
extrapolations to different operating conditions cannot be
trusted. Vendors of MDEA-based solvents such as Dow and Union
Carbide use proprietary rate-based simulation programs that are
based on extensive collections of proprietary data to predict the
performance of their solvents. Anyone who wishes to evaluate the
performance of MDEA for a selective HzS removal application
should work with a solvent vendor to obtain performance
estimates.
Although Simulation Sciences' PRO/II contains an amines data
package, it gives very poor results for amine units and should
not be used for simulating them. PRO/II's inability to model
amine units is due to problems with both the equilibrium data in
the data bank and the algorithm that PRO/II uses to solve amine
absorbers and strippers. A PRO/II simulation of the Carter Creek
Gas Plant does predict the performance of its amine units
accurately. However, this simulation was created by Simulation
Sciences with built-in adjustable parameters that were fitted to
actual plant data. These parameters are not available in
standard versions of PRO/II's amines data package.
8.2

Bow to create a Simulation of an Bxisting Amine unit

A simulation of an amine unit on TSWEET or Hysim can be made to


match plant operating data by using the number of theoretical
stages in the absorber and stripper as adjustable parameters.
Before creating the simulation, the following plant data must be
collected:

Feed gas composition(s) and conditions


Product gas composition(s) and conditions
Amine circulation rate(s)
Temperature of lean amine feed to absorber(s)
Flash drum temperature and pressure
Rich amine temperature leaving lean/rich exchanger
Pressure at top and bottom of stripper
Pressure and temperature of reflux drum
Acid gas flow rate and composition
Stripper reboiler duty or reflux ratio (both if possible)
Lean amine loadings of HzS and COz

PROCESS SIMULATION

8.Z

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

A value for the rich amine loading must also be determined. It


is difficult to obtain good samples of rich amine solutions,
since rich amine evolves acid gas rapidly when its pressure is
reduced in the course of sampling and analysis. This introduces
a source of error in any analytical measurement of the loading.
This property of rich amine solutions also makes them hazardous
to handle. As a result, a calculated value of the rich loading
is normally used. The rich loading can be determined easily
based on the circulation rate, lean loading, and the quantity of
acid gas removed in the absorber or evolved in the stripper.
(Note that if the flash tank temperature is higher than 150 0 F, or
if the pressure is only a few psig, enough acid gas may be
evolved there to make a significant difference in the rich
loading.)
Once the input file has been created, the number of theoretical
stages in the absorber and stripper should be adjusted until the
best agreement is found with the plant performance data. This
number of theoretical stages is entered directly into TSWEET. In
AMSIM (HYSIM), it is done indirectly by entering the number of.
actual trays and tray efficiencies. In most amine units, a 20
tray absorber will contain around 5 theoretical stages. A packed
absorber with a 20' packed section will contain roughly 2
theoretical stages. A 20-25 tray stripper will contain around 7
theoretical stages including the reboiler and condenser. The feed
stage is normally the third stage from the top.
The number of stages in the stripper should be adjusted until
good agreement with the measured lean loading is obtained. When
adjusting the number of stages in the stripper, the number of
stages between the feed stage and the reboiler should be
adjusted. If values are available for both the reboiler duty and
reflux ratio, the number of stages should be adjusted until
agreement is found between these measured values and the
simulator predictions. This provides a more accurate model of
the number of stages in the stripper.

The number of stages in the absorber should be adjusted until


good agreement with the sweet gas composition is obtained. In an
absorber containing fewer than 4 stages, the roundoff error
associated with having to use the closest integer number of
stages will become significant. Unfortunately, TSWEET does not
allow fractions of stages to be used. In these applications,
AMSIM (HYSIM) i~ recommended because any fractional number of
stages can be used simply by adjusting the tray efficiencies.
8.3

TSWEET

TSWEET is produced by Bryan Research and Engineering of Bryan,


Texas. It is a specialized simUlation program designed to
PROCESS SIMULATION

8.3

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

simulate amine units and Claus sulfur recovery plants. Although


it is an equilibrium stage model, it contains a kinetic model for
CO 2 absorption in the absorber. This is supposed to provide
accurate predictions of the performance of MDEA for selective H2S
removal.
TSWEET's kinetic model is based on the residence time for liquid
on each tray. This must be calculated by the user and supplied
as input. In most amine absorbers, the residence time is
approximately two seconds. TSWEET defines the liquid residence
time as follows:
Residence Time

(Tray Bubbling Areal * (Weir Heightl*(Froth Gravity)


Liquid Flow Rate

The froth gravity is normally around 0.30-0.35 for amine systems.


A better method for estimating the liquid residence time can be
found in a 1985 Chevron Research Company report (reference 9.4).
However, the liquid residence time is normally adjusted manually
by the user in order to match the simulation results to plant
data. As a result, most users will simply start with an initial
guess of two seconds rather than taking the time to calculate
this parameter.
TSWEET offers the capability to simulate liquids treaters as well
as gas absorbers. TSWEET's approach is to create a gas phase
with which the amine and liquid hydrocarbon phase both reach
equilibrium. By adjusting the number of theoretical stages,
agreement can be obtained with plant performance data. However,
the number of stages in a liquids treater is typically between
one and two; as a result, a significant error may result from the
need to use an integer number of stages in TSWEET. Even if
agreement is obtained with plant data, extrapolations to
different operating conditions should be made with caution. The
HETP values or tray efficiencies in the treater are sensitive to
hydrocarbon and amine circulation rates.
8.4

AKSZH (or HYSZH)

D. B. Robinson and Associates of Calgary created the AMSIM


process simulation program for amine units. Although it is sold
as a stand-alone program, it has been incorporated into
Hyprotech's HYSIM process simulation program. The data and the
. calculation routines in HYSIM's amines data package are
essentially identical to AMSIM.
Like TSWEET, AMSIM is an equilibrium stage model. Unlike TSWEET,
however, it offers the option of calculating tray efficiencies
for H2S and CO2 based on mass transfer correlations and tray
design parameters. This allows the absorber and stripper to be
PROCESS SIMULATION

8.4

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

simulated with different numbers of theoretical stages for H2S


and CO2 , and is the main advantage of AMSIM over TSWEET. The
user must provide values for the tray diameter, the weir length,
and the weir height. Based on these values, tray efficiencies
are calculated using a mass transfer-based correlation.
Necessary values for mass transfer parameters are included in
AMSIM's data base. The user can also input tray efficiency
values. If the user does not provide any efficiency values or
tray parameters, AMSIM will use 1.0 as its default efficiency
value for both CO2 and H2S.
Although AMSIM is a better model than TSWEET from a theoretical
point of view, it is more difficult to use. The stand-alone
version of AMSIM has a poor user interface that, among other
things, does not allow the user to save an input file until it
has been completed. Some mistakes in data entry cannot be
corrected without exiting the program and losing the entire input
file. HYSIM does not have these problems, although it is more
difficult to get a stripper to converge than most other
distillation columns. In order to make a stripper converge, the
damping factor should be adjusted to no more than 0.4 from its
default value of 1.0. An initial temperature profile should be
provided: at a minimum, the top tray and condenser temperatures
need to be provided.
Unlike TSWEET, which automatically calculates the water make-up
requirement, a HYSIM user must add the make-up water in a
separate unit operation. This is done by using a "Mixer"
operation with the specification that the flow rate of water
leaving the mixer is equal to the amount of water in the lean
amine feed to the absorber. The water make-up is calculated
automatically in the stand-alone version of AMSIM.

PROCESS SIMULATION

8.5

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES RESOURCE GUIDE

REFERENCES

8.1

Hyprotech, Inc., HYSIX special Features and Applications


Guide, Version C2.10, January, 1993.

8.2

Bryan Research and Engineering, Inc., BR&E Graphics, TSWEET,


and PROS IX Osers' Guide, Version 93.0, March, 1993.

8.3

Robb, D. A., Chevron Research and Technology Company report,


"Evaluation of Amine Plant simulation Packages", dated March
13, 1991.

8.4

Swanson, D. S., Chevron Research Company report, "Guidelines


for Using the TSWEET Simulation Program", dated February 4,
1985.

8.5

Swanson, D. S., Engineering Technology Department report,


"TSWEET Technical Limitations and User Guidelines", dated
January 21, 1988.

PROCESS SIMULATION

8.6

JULY 1994

AMINE TREATING BEST OPERATING PRACTICES GUIDE

9.0 TROOBLESHOOTING

This section contains a general guide, "Troubleshooting Amine


Units". The guide is intended to provide information in summary
form that is also explained in more detail in other portions of
the "Amine Treating Best Operating Practices Guide".

TROUBLESHOOTING

9.1

JULY 1994

'.

TROUBLESHOOTING AMINE UNITS

Remedies

Page 1 of 7

Remarks

Problem

Possible Cause

1. High H2S Content in


Sweet Gas from Absorber

A.Low lean amine feed rate.

A.

Increase amine rate.

A.May need an updated analysis of


the acid gas content of the sour
gas.

B.High lean amine


temperature.

B.

Lower temperature until lean


amine is only 10-1S o F warmer
than sour gas feed.

B.Lower temperatures improve H2S


absorption. Lower temperatures will
inhibit COS hydrolysis.

C.Poor amine regeneration.

C.

D.Foaming in absorber.

D.

Add antifoam.

E.Weeping in absorber.

E.

Maintain minimum gas rates to


avoid weeping.

E.Low gas rates reduce gas/liquid


contacting efficiency.

F.Flooding in absorber.

F.

Keep sour gas feed rates and


lean amine rates below flood
limits.

F.Flooding entrains rich amine as


does foaming.

G.Tube leak in lean/rich


exchanger.

G.

Repair tube leaks.

G.Analyze lean loading of amine in


and out of lean/rich exchanger.

A.See B-D below.

A.

Add antifoam until signs of


foaming have stopped. For
short-term use.

A.Foaming is indicated by high


column pressure drop and/or rapid
filling of reflux drum or absorber
overhead knockout drum.

2. Foaming in Absorber
(high pressure drop
across absorber)

See Problem 3.

C.Lean amine loading should be less


than the equilibrium loading needed
to achieve acid gas content of the
sweet gas.
See Problem 2.

D.Foaming entrains rich amine into


upper trays of the absorber adversely affecting H2S removal.

Antifoam is removed by the charcoal


beds. The beds are deactivated by
antifoam reSUlting in more frequent
replacement.
B.Hydrocarbon liquids
accumulation in absorber.

B.1

Skim hydrocarbon layer from


approprate vessels.

B.2

Ensure that lean amine


temperature is at least 1015F greater than sour gas
feed temperature.

B.Hydrocarbon liquids may be


detected by checking sight glasses
in appropriate vessels.

TROUBLESHOOTING AMINE UNITS

Problem

Possible Cause

C.Solids accumulation in
amine system.

D.Accumulation of amine
degradation products or
other surfactants.

E.Sudden increases in gas


flow rate to absorber.

Remedies
B.3

Check condition of inlet


filter/separator filter
elements.

B.4

Check condition of activated


carbon; beds may need
backwashing or replacement.

B.5

Check hydrocarbon content of


amine drips returned to
process.

C.1

Check amine filter operation.

C.2

Check inlet filter/separator


filter condition if there is
one in the system.

D.1

Maintain heat stable salt


concentrations less than 5-10%
of active amine. (Purge amine
if necessary.)

D.2

Excessive use of corrosion


inhibitors can cause foaming.

E.

Make feed rate changes


gradually. Be prepared for
upsets during upstream
irreqularities.

Page 2 of 7

Remarks

C.Solids content should be less than


10-20 ppm (wt) and amine should be
bright and relatively clear.

D.Check surface tension and conduct


foaming tests on a regular basis.

TROUBLESHOOTING AMINE UNITS

Page 3 of 7

'.
Problem
3.

Poor Amine Regeneration

Remedies

Possible Cause

Remarks

A.Low reboiler steam rates. I A.

Provide 1.0-1.5 Ib steam per


gal. of lean amine fed to
absorber, to ensure adequate
stripping of H2S and C02.

8.High regenerator
pressure.

B.

Decrease pressure controller


set point.

C.Foaming in regenerator.

C.

See Problem 2.

C.Foaming indicated by high


regenerator pressure drop.

D.Flooding in regenerator.

D.

Reduce steam rates to


reboiler.

D.Flooding indicated by high


regenerator pressure drop.

E.Weeping.

E.

Increase steam rates to


reboiler.

F.Poor feed rate control.

F.l

Tune level controller to


provide relatively smooth feed
rate while allowing more
fluctuations in flash drum
level.

F.2

Alternatively, use a flow


controller with a set point
adjusted by the flash drum
level controller.

G.Leaking lean/rich
exchanger.

G.

Make necessary repairs.

G.Sample lean amine upstream and


downstream of lean/rich exchanger
and compare acid gas loadings to
determine if leakage exists. Must
cool sample from regenerator bottoms
to prevent loss of H2S from hot
sample.

H.Incorrect reading from


amine analyzer.

H.

Check and recalibrate H2S in


amine analyzer.

H.Analyzer may need frequent


recalibration.

,3

A.Analyze lean amine for acid gas


content, (lean loading).

TROUBLESHOOTING AMINE UNITS

Possible Cause

Problem
4. Amdne Contamination

A.Degradation of amine.

Remedies

Page 4 of 7

Remarks

A.l

Check activated carbon filter


operation. Backwash it or
repll!lce carbon.

A.l Activated carbon filter should


absorb organic-based degradation
products.

A.2

Maintain low regenerator


pressure to minimize thermal
degradation.

A.2 Amdne will thermally degrade if


steam pressure is >50 psig on
reboiler.

A.3

If solution appears brownish,


check thio-sulfate content and
operation of amine storage
tank blankets.

A.3 Oxygen entering the storage


tanks will react with the sulfides
in the amine solution to form
thiosulfates and impart brownish
color.

B.Solids.

B.

See Problem/Remedy 2.C.

c.

C.

Liquid hydrocarbon.

See Problem/Remedy 2.B.

A.Pressure control valve


100% open.

A.

Increase pressure set point


slightly.

B.Poorly tuned pressure


controllers

B.

Retune.

C.Liquid carry-over from


reflux drum.

C.

Check reflux drum level.


System may be foaming or
flooding. See Problems 3.C
and 3.D.

C.Liquid carry-over in line could


affect gas flow through pressure
control valve.

6. Reflux Drum OVerhead


Gas Develops High Back
Pressure

A.Flow limits in
downstream.

A.

Take steps to address


downstream problems and reduce
gas plant feed rates.

A.High reflux drum pressure may


activate emergency backup treating
systems.

7. Amine Carry-OVer from


Reflux Drum

A.Foaming.

A.

See Problem 3.C.

B.Floodinq.

B.

See Problem 3.D.

5. Poor Regenerator
Pressure Control

A.Do not raise regenerator overhead


pressure above 20 psig, if possible,
since this adversely affects H2S
stripping.

TROUBLESHOOTING AMINE UNITS

Problem

Possible Cause

Remedies

Page 5 of 7

Remarks

8. Steam Rate Too Low to


Reboiler

A.Steam temperature is too


low to provide adequate
reboiling; or condensate
system is backing up.

A.

Increase steams ide pressure by


adjusting set point. When
pressure must be increased to
above 50 psig, reboilers may
be fouled and need cleaning.

9. Poor Control of Lean


Amine Cooler OUtlet
Temperature

A.Amine cooler bypass is


100% open but amine is
still too cool

A.

Pinch back on lean amine


cooler outlet valve.

lO.Amine Strength Less Than


or Greater Than Target
Value

A.Incorrect make-up water


or steam rate to
regenerator.

A.

Adjust make-up rate to


compensate.

11.Low Lean Amine Storage


Tank Level

A.High levels in process


vessels.

A.

Adjust levels and recheck lean


amine storage tank.

A.
Check to see if losses are
within guidelines.

B.Low solution inventory.

B.

Make up additional solution

B.Check for leaks, open drain valve,


etc.

A.Low levels in process


vessels.

A.

Adjust levels and recheck lean


amine storage tank.

12.High Lean Amine Storage


Tank Level
13.High Pressure Drop
Across Amine Charcoal Bed
or Filter Media

A.Excess feed rate to


media.

I A.

Open media bypass slightly.

A.Maintain design flow rate through


media. If design flow rate and
pressure drop cannot be maintained
it is time to change the media.

B.Partially plugged media.

I B.

B.Media may plug with solids or wax.

A.

Backwash media with hot water


or replace. Alternatively,
open top and steam downwards.
Try tuning controllers to
provide smoother flows and
allow more fluctuations in
regenerator bottoms level.

A.Poor backwashing.

A.

Increase backwash time.

B.High solids loadings.

B.

Check filter solids removal


efficiency.

C.Wax buildup on elements.

C.

Remove elements and steam


clean manually.

14.Fluctuating Filter Feed


Rates
A.Fluctuating control valve
position.

1S.Frequent Filter
Backwashing

A.Do not exceed 50 psig steam


pressure. This results in high
reboiler tube temperatures and
increased amine degradation.

TROUBLESHOOTING AMINE UNITS

Problem
16.High Corrosion Rates in
Amine Loop

Possible Cause

Remedies

Remarks

A.Solids level too high.

A.

Improve filter operation.

A.Solids have erosive effect which


also accelerates corrosion rates.
Solids levels should normally be 1020 ppmw or less.

B.Amine strength too high.

B.

Add make-up water to


inventory. Adjust steam makeup rate to regenerator.

B-E:Corrosion rate is increased by


high amine strength, high H2S
loading, and high concentrations of
heat-stable salts. Also, chloride
stress cracking may occur if
chloride levels exceed about 500
ppm.

C.High acid gas content in


rich amine.

C.

Increase amine circulation


rate.

D.High level of heat stable I D.


salts.
I E.

E.High chloride level.

17.Hydrate Formation Hydrate crystals Plug


Instrument Leads

Page 6 of 7

Bleed off some amine for


disposal. Make-up with fresh
amine.
Bleed off some amine for
disposal.

F.Generally corrosive amine I F.


despite good operation.

Inject corrosion inhibitor


into amine system. Consider
replacing amine solution.

A.Instrument leads around


an inlet filter/separator
too cold.

Check steam tracing.

A.

,..

,"

I'

".
;1

TROUBLESHOOTING AMINE UNITS

Page 7 of 7

'.
Problem
lS.Excessive Acid Gas
Released in Flash Drum

Possible Cause
A.Rich loading in rich
amine is too high.

Remedies
A.

Increase amine circulation


rate to the absorber.

Remarks
A.Vent gas H2S content may exceed
specification (excess sulfur might
show up further downstream in fuel
gas or flue gas). Routine analysis
of the flash gas would reveal this.
Increased amine circulation rate
will lower rich loading but increase
regeneration energy use.

19.High Hydrocarbon content


in Acid Gas Product

B.

Raise Flash Drum pressure (See


19.A)

B.Raising the Flash Drum pre~sure


also reduces the amount of
hydrocarbon vaporization, thereby
increasing the hydrocarbon content
of the acid gas to the SRU.

A.High pressure in Flash


Drum.

A.

Pressure should typically be


150 psig or less.

A.High pressure reduces flashing of


absorber hydrocarbon. Any
hydrocarbon remaining in the rich
amine will end up in the acid gas
product the SRU.

B.Circulation rate is too


high.

B.

Review design vs. operating


conditions for Flash drum.

B.High circulation rate reduces


residence time in flash drum and can
cause hydrocarbon carry-under.

C.Foaming in the Absorber.

C.

See 2.A-D.

C.Absorber foaming can cause


hydrocarbon entrainment into the
rich amine.

D.High hydrocarbon content


in rich amine from
absorber.,

D.

See 2.B.

D.Absorber foaming, hydrocarbon


condensation in the absorber and
poor level control can cause
entrainment in the amine.

BEST PRACTICE FOR HYDROCARBON AND PARTICULATE REMOVAL FROM


AMINE SYSTEMS
Introduction
Poor solvent quality is the most common cause of operating problems within amine units. The three major
contaminants which have a significant detrimental impact on solvent performance are heat stable salts (HSS),
hydrocarbons (free and dissolved) and particulates. Heat stable salts increase corrosion rates and reduce the amount
of amine available for acid gas pick-up. Both hydrocarbons and particulates increase foaming which has been
identified as the most frequent cause of off spec gas and high amine losses in Chevron facilities. High particulate
levels are also responsible for increased corrosion rates in some amine units. A separate best practice exists for HSS
control. A best practice for hydrocarbon and particulate control has been developed on the basis of a survey of 21
upstream and downstream Chevron facilities, input from some vendors and a literature search. Some non-Chevron
industry operators were invited but declined to participate. A summary and consolidation of the survey results is
attached as an appendix. The number of incidents of off spec gas per volume of gas processed or per volume of
amine circulated has been used as rough qualitative indicator of performance in comparing practices.
Due to wide variations in process feed quality and conditions each unit should be considered somewhat unique and
it is inappropriate to prescribe a single set of best practices for all facilities. This is illustrated by the differences
between upstream and downstream facilities. The former usually have cleaner feed gas but also have much tighter
sweet gas specifications and so are more sensitive to amine contamination. Thus what is considered "best practice"
for an upstream facility may be quite different from a downstream facility "best practice" where problems and
constraints differ. In light of this, the best practice is presented as a three level approach where effectiveness,
stringency and cost increases from level I through to level 3. It is the responsibility of the unit engineer to determine
which level constitutes best practice for a given facility. If adherence to level I practices do not adequately address
operating problems then levels 2 or 3 should be considered. Each level is considered additive to the preceding so
that adherence to a specific practice level assumes compliance with the preceding levels of practice.
The best practice is broken down into three elements or components; free or entrained hydrocarbon control /
removal which deals with inlet gas scrubbing and hydrocarbon skimming; dissolved hydrocarbon / organics
removal which deals with activated carbon systems; and particulate removal which addresses mechanical filtration.
There are three levels of best practice for each component. Which level of practice constitutes "best" at a given
facility may vary for each component and specific practices within the component. A unit may require only level 1
practices with respect to hydrocarbon removal but level 3 practices for particulate handling. The three elements of
the best practice are interdependent and must not be considered alone. For example, by improving free or dissolved
hydrocarbon removal from amine, foaming tendencies are reduced and so it may be possible to tolerate higher
particulate levels without any detrimental impact on performance. The specific recommended practices for each
component are discussed below and summarized in a table along with the rationale for the recommendations and
symptoms to look for in diagnosing a problem.

Component 1 - Free and Entrained Hydrocarbon Removal

Amine contamination with free hydrocarbon is a frequent cause of foaming in the treater and the absorber and it's
symptoms are described in the summary table. Sources offree hydrocarbon include entrainment or slugging of
process liquids (or lube oil) with the feed gas and condensation in the gas absorber. Condensation in the treater is
controlled by maintaining the lean amine temperature at least 10-15 fO above the gas temperature (see Amine
Treating Best Operating Pra~tices Resource Guide). Strategies to control free hydrocarbons in the amine should
focus on prevention (i.e. adequate inlet knockout facilities) but also need to address removal (skimming) since some
contamination is inevitable. In some cases upgrading of the skimming facilities may be more economic than
upgrading inlet knockout equipment.

Level 1 Practice
Minimum recommended hydrocarbon control/removal facilities for Chevron amine units consist of:

gas inlet knockout drum with automatic level control, demister and high level alarm; this may simply be part of
the plant inlet separation train (upstream facilities) or part a dedicated vessel in the amine unit

manual hydrocarbon skimming system on flash drum consisting of sight glass, nozzle and valve (pump may be
required if flash drum operates at low pressure)

These are the minimum facilities reported in the survey that appear to be performing adequately. Sizing of the inlet
knockout drum with respect to liquid slug handling is critical to the overall performance of the amine unit. Both
gravity and centrifugal (PortaTest) separators are used successfully. Adequate skimming facilities are also critical to
good unit performance. Of the 21 units surveyed, 6 do not have or use skimming systems and of these 5 are in the
lowest third of performance as measured by incidents of off spec gas per volume of gas throughput or amine
circulated. The flash tank/drum is the most appropriate location for skimming in that it permits removal of the free
hydrocarbon upstream of the regenerator. Some vendors use multiple nozzles at various levels in the vessel to
simplify skimming (avoid having to raise and lower liquid levels). Vendors recommend a residence time of at least
20 - 40 minutes to permit hydrocarbon separation. The richer the inlet gas (or the more entrained liquid) the longer
the required residence time. Free hydrocarbon in samples of rich amine downstream of the flash drum are indicative
of inadequate separation due to limited residence time, insufficient skimming or poor flow patterns. Temperature
and pressure should be as high and low as possible respectively to promote hydrocarbon separation and
vaporization.

Level 2 Practice
If the level I practice is inadequate to control the free hydrocarbon content of the amine, determine the source of the
hydrocarbon. If entrainment is a significant source consider use of coalesor filter / separator on the inlet gas if the
inlet knockout drum cannot be modified to remove the entrained liquid. Typically coalesor filters / separators are
used when droplet size is < 3 11. If liquid volumes are small and there is little slugging coalesor filter / separators
may be used in place of a conventional inlet knockout drum. In most cases however vendors recommend use of the
coalesor unit downstream of the knockout drum.
If the source of the hydrocarbon is due to periodic carry over from the inlet knockout, and both upgrading of this
vessel or modifying upstream operations are impractical, then consider use of multiple skimming locations. This
permits removal of hydrocarbons that may get by the flash drum and concentrate elsewhere in the system. Survey
results indicate that such designs can be beneficial to overall performance; of the top seven performers five had
mUltiple skimming locations. Recommended skimming locations are listed in the summary table. In general, the
closer to the treater the better (i.e. catch the hydrocarbon before it gets too far).

Level 3 Practice
If level 2 practices do not control free hydrocarbons focus efforts on eliminating the source. If this is not possible
use of automated skimming system using bucket and weir internals should be considered. This will permit
continuous hydrocarbon removal. Chevron has not had any experience with such systems however vendors indicate
that these systems have proven effective in commercial operations. Typical designs are presented in the Chevron
Pressure Vessel Design Manual, Figure 900-14 or Lieberman "Troubleshooting Natural Gas Processing" Figure 12-

4.

Component 2 - Dissolved Hydrocarbon I Organics Removal (Activated Carbon Systems)


Similar to free hydrocarbon, dissolved hydrocarbon or organics can cause foaming with the associated operational
problems as summarized in the table. In addition the dissolved material may be organic acid precursors of heat
stable salts (HSS) which in tum contribute to corrosion and declining amine unit performance. Sources of these
material include process liquids, corrosion inhibitors, antifoam chemicals (if in excess), other process / treatment
chemicals (well treatment, demulsifier etc.), detergents used during shutdowns and to treat cotton filter material.
Detection is more difficult due to the small quantities present. Other than eliminating the source, activated carbon is
the common method of removing these materials.

Levell Practices
The minimum recommended practice is no carbon system. Many amine units operate acceptably without it. Of the
21 units surveyed 6 either did not have or use a carbon system and there was no apparent impact on unit
performance. Many of these units did report however that they had used carbon on a temporary basis to clean up
their amine. Of note is that essentially all the upstream facilities (gas plants) have carbon systems although it is out
of service at one of the plants. This likely reflects a greater need for carbon in upstream units due to more stringent
sweet gas specifications and the impact of field operations. While no carbon may be acceptable for some existing
facilities it should not be assumed for new designs, particularly upstream gas plants, since more likely than not
carbon will be required.

Level 2 Practices
The level 2 practice consists of some form of activated carbon treatment on the lean amine stream. There are a
variety of activated carbon systems in use (cartridge, mixed with filter precoat, beds), most of which are reported to
be performing adequately and so no specific types are recommended unless there are operational problems (see
level 3 practices). The recommended location is after the particulate filters preferably downstream of the coolers and
charge pump. These are the optimal conditions (low temperature and high pressure) in the circuit for adsorption.
Dow Chemical noted that for most amine systems a temperature of 120 - 150 OF is recommended to avoid viscosity
problems in the carbon system.
Other recommended practices are to avoid steam regeneration of carbon on small to mid-size carbon systems, to
monitor either color or corrosion inhibitor residuals to determine when changeout is required and to follow carbon
suppliers procedures for changeout. In several cases steam regeneration was reported to have resulted in a release of
carbon fines into the amine. In most cases the savings realized through regeneration do not justify the risk of amine
contamination. With respect to carbon change out some operators reported dP across the unit as the basis of
changeout, however this is only an indicator of solids accumulating on the carbon or amount of fines accumulation
and carbon may become saturated long before any significant change in dP is observed. Other operators report that
change out is simply every 1-2 years and is not based on amine or unit performance monitoring. Again, it is likely
that the carbon will be saturated before change out occurs. Lastly carbon changeout procedures must be emphasized
since performance is very sensitive to loading procedures. Depending upon the type of carbon system vendor
procedures should include some or all of the following; 12 - 24 hour water presoak, loading in slurry form and back
washing to eliminate carbon fines.

Level 3 Practices
Level 3 practices consist of a consolidation of vendor design practices for the three common type of carbon systems.
These are tabulated below and should be viewed as guidelines against which existing operations can be compared
and new facilities can be designed. Of the facilities surveyed graded beds were the most common. These are
generally recommended over cartridge or deep bed units. Cartridge units have a shorter life and so are more prone
to saturation prior to change out. Deep beds combine particulate filtration with carbon treatment and as result use
softer carbon due to it's lower density. This, in conjunction with higher velocities tends to result in a significant
number of carbon fines being generated and released into the amine if downstream filtration is not used.
Furthermore coal based carbon is recommended over wood based material since it has a higher adsorption capacity
and a broader distribution of micro pore sizes as well as being harder. Parallel beds should be used so that one bed is
available for service when the other is being changed out. A maximum bed life of six months is recommended.
Lastly, particulate filtration downstream of the carbon unit is recommended to prevent contamination of the amine
with carbon fines (see Particulate Filtration).

Carbon System Design Guidelines


Carbon Mesh
Carbon Density (lb/ff)
Type Of Carbon
Empty Vessel Residence Time (min.)
Superficial Amine Velocity (gpm/ft2)
Bed Life (months)
Amine Slipstream Size (% total flow)

Cartridge
10 x 22
30
Carbon based
<15
I-2
<2
10 - 20

Graded Bed
10 x 30
30
Carbon based
15 - 20
2-5
2-6
10 - 20

"Deep" Bed
4 x 14
17
Wood based
20 - 30
10 - 15
6 - 12
25 - 100

Component 3 - Particulate Filtration


Particulate contamination is of concern in amine units because it promotes both corrosion and foaming. Corrosion is
promoted by the particulate erosion of the passive layer on metal surfaces. This is primarily a function of the total
suspended solids (TSS) concentration and to a lesser extent by the composition or hardness of the particles. In
foaming, particulates have a secondary role of stabilizing foams by reducing surface tension. They do not directly
cause foaming. As a surface active agent their influence depends on particle size and composition as well as TSS
concentration. All these characteristic should be considered when determining what constitutes "best practice" for a
given unit. For example a 150 ppm TSS contamination may be acceptable if particles are > 5 !.t while a TSS of 50
ppm may be total unacceptable if particles are < 2 !.t. Particulate sources include FeS and other fines entrained with
the inlet gas, FeS and iron oxides generated by corrosion within the unit, amine degradation products and carbon
fines. Most of these particles are> 1O!.t in size except carbon fines and FeS which are 1-3 !.t and < I !.t respectively.
In all cases source control/elimination should be considered before upgrading filtration facilities.

Level 1 Practices
As outlined in the summary table level 1 practices consist of particulate filtration on a 25 - 50% slipstream.
Although a few units surveyed reported a smaller slipstream it is notable that some of these units are also
experiencing operating problems due to particulate contamination. Vendors recommend a maximum TSS loading of
150 - 200 ppm however this should be adjusted on the basis the particle characterization. Upstream gas plants which
often experience high FeS (small particles) levels typically target a significantly lower TSS level. A 25 !.t nominal
rating is recommended. This will actually pass particles up to 40 - 50 !.t so is consistent with the maximum reported
values.
A variety of filter types were reported in the survey and there are no clear recommendations in the literature.
Acceptable types include sock, cartridge, bag and leaf. Backwashable systems have only had minimal success.
Selection of a specific type will depend upon rates, required size, filter life and cost. In general bag and sock units
should be considered for bulk removal of larger (> 5 !.t) particles at high rates and cartridge units used for smaller
flow rates 500 gpm) and smaller particles.
Theoretically rich amine filtration should be more effective than lean amine filtration since it permits removal of
particles before they can "hang up" in the regenerator, surge tank etc. Survey data does not support this however;
plants which filter rich amine do not appear to have better performance than those that filter lean amine. Although
this may be a reflection of other factors it does indicate that there is no clear justification for the increased risk
associated with rich filtration.

If the primary particle source is entrainment in the inlet gas and droplet size is 0.5 - 3 !.t an inlet filter separator
should be considered.

Level 2 Practices
Level 2 practices are similar to level 1 except full lean flow filtration is recommended to permit more rapid particle
removal rates. A particle characterization (size distribution and composition) should be completed to permit
adequate filter sizing and TSS targeting as well as identifying the source for control/elimination. Initial sizing of25
!.t absolute and target loading of 30 ppm are based on data from the upstream gas plants.
Level 3 Practices
Level 3 practice consists of a dual filtration system. A bulk filter (either sock or bag) upstream of the carbon units
removes the majority of the larger particles. These must be sized to protect the carbon units from plugging with
particles. A smaller unit, typically a cartridge filter although others can be used, filters on the slip stream coming out
, of the carbon unit. The slip s~eam filter should be sized to remove any entrained carbon particles, typically> 5 !.t.
This design permits removal of the smaller particles without the high capital and operating cost of small micron full
flow filtration

SUMMARY TABLE OF BEST PRACTICE FOR HYDROCARBON AND PARTICULATE CONTROL / REMOVAL IN AMINE SYSTEMS
(see text for more detail)

Level 2

Levell
Best Practice
Component
Free Hydrocarbon
Control I Remo\"al

Symptoms Of A Problem
Any or all of the followmg. symptoms may be
indicating. thai the e)(isling free hydrocarbon
removal practices are inadequate and should be
upgraded:

foaming as indicated by high .lP across columns


(> than 40% of height between top and bottom
tray (in feel of water)), offspec sweet gas or
e:-::cessive amine losses (> 3 IbsIMMSCF)
erratic liquid le\'els in vessels or column sumps
visible hydrocarbon level in absorber sump" flash
drum or reeenerator reflux accumulalOr with
frequent skimming required
visible hydrocarbon layer on amine sample
amine carryover to SRU or in sweet gas

Dissolved
Hydrocarbon I
Organics Removal
(Carbon Systems)

Any or all of the following symptoms may be


indicating that the existing dissolved hydrocarbon I
organic removal practices are inadequate and should
be upgraded:
foaming as described above
odor of hydrocarbon on rich amine sample but no
visible layer
high rate ofHSS fonnation from organic acid
precUl'Sors as indicated by high corrosion rates (>
10 mpy for carbon steel & 5 mpy for SS) and I or
translucent black amine (FeS particles from
corrosion)

Recommended Practice

Rationale

gas inlet knockout drum with automatic


level control. demisler and high level alarm:
this may simply be pan of the plant inlet
separation train (upstream facilities) or part a
dedicated vessel in the amine unit

some type of liquid hydrocarbon removal


upstream of the treater is essential to
minimize foaming in the treater and a
simple knockout drum is the most COSI
effective method of doing this
all facilities surveyed had some form of inlet
lcrtockout, either as pan of an plant inlet
separation train or a vessel dedicated to the
amine unit
some amount of hydrocarbon contamination
is inevitable for most facilities so a
skimming system is necessary to remove the
hydrocarbon once it is in the amine
5 out of 21 facilities surveyed had no
skimming facilities on the flash drum and all
these were in the lowest third of plant
perfonnance as measured by incidents off
spec: gas per either gas throughput or amine
circulation rate
the rich amine flash drum is the most
appropriate location for skimming since it is
upstream of the regenerator and can be
designed with sufficient residence time 10
pennit hydrocarbon sepanttion

use coalesor filler I separator on inlet (after


knockout drum) ifenlrainmenl from inlet
knockout is a problem

5 of 21 facilities surveyed do not have or


use a carbon system and of these 4 are in the
top third of performance as measured by
incidents off spec gas per either gas
throughput or amine circulation rate
although no carbon may be acceptable for
some facilities this is not recommended for
new designs since il is more likely than not
that earbon will be required

activated carbon system on lean amine


downstream of mechanical filtration, lean
amine coolers and after charge pump

manual hydrocarbon skimming. system on


flash drum consisting. of sight glass. nozzle
and valve (pump may be required if flash
drum operates low pressure)

no activated carbon system

Any or aJl of the following symptoms may be


indicating that the existing particulate control I
removal practices arc inadequate and should be
upgraded:
foaming as described above
translucent to opaque amine samples (green color
may indicate finely divided FeS I "'), black
color may indicate larger FeS panicles or carbon
fines)
sedimentation in amine samples
high corrosion rates (> 10 mpy for caroon steel
and > 3 mpy for stainless steel)
plugging of instrumentation taps

paniculate filtration on a minimum 2550% slip lean amine stream

maximum TSS of 150 - 200 ppm


maximum 25", nominal rating

changed out on basis of high .1P


use inlet fiher sepanttor if most panicles arc
entrained with inlel gas and particle size is
0.5 -3"

particulate filtration is aJways required doe


10 corrosion generation of particles
lean fihrarion preferred for safety reasons
and there is no clear evidence that rich
filtration improves performance
minimum slip stream recommended in
lilenttwe, most surveyed facilities had slip
streams of 50 - 100%
TSS level recommended by chemical
vendors
maximum reported size thaI appears to be
doing an adequate job and also vendor
recommendation
.1P is measure of effective filter life

pennits removai of particles before they


reach lreater

(Recommended practices are in addition to Levels I and 2)


Recommended Practice
Rationale

coalesor filter I separator can remove


entrained liquid and paniculales which are
nOI eliminated by the knockout drum (i.e.
< 3 J.l)
recommended in literature and is standard
design for many vendors (TPA. Pritchard,

use a bucket and weir system for hydrocarbon


skimminl! in the flash drum with automatic
level control (see Chevron Pressure Vessel
Manual Figure 900~14 or Lieberman
""Troubleshooting NaMal Gas Processing""
Figure i2-4 for typical design)

ensures that hydrocarbons are continuously


removed

size cari>on system for a minimum of a 10


2Q1'10 slipstream flow

less than 10..20% slipstream flow is


ineffective in maintaining low dissolved
hydrocarbon levels in most amine systems

etc.)

use multiple skimming locations; pOlential


locations (in order of preference) are flash
drum" absorber sump, regenerator reflux
accumulator. regenerator sump, and amine
surge lank

multiple locations maximize the


opponunity for hydrocarbon removal
out of 21 facilities surveyed 6 used
multiple skimming locations and 5 of these
facilities were in the top third performers
as measured by incidents ofT spec gas per
either gas throughput or amine circulation

",'e

carbon treatment of rich amine nor


recommended due 10 higher likelihood of
saturation by free hydrocarbon and
reduction adsorption due to acid gas
breakout
place dovmSlrcam of mechanical filters to
avoid plugging carbon system with solids
high pressure and low tempel'llture (120 150 oF) inCRases adsorption

stearn regeneration not recommended

facilities Ihat have used steam regeneration


reported problems with carbon fines in

monitor amine color or corrosion inhibitor


residuaJs to determine when changcom
required ~ do not use .1P or only change out
when convenient
follow carbon suppliers loading procedures
including water soak., slurry loading and
backwashing: to remove carbon fines
paniculatc filtration on full flow lean amine

some units monitor.1P or only changcout


once every 1-2 years and do not determine
if carbon is spent

system

Particulate Control I
Removal

Level 3

(Recommended practices are in addition to Levell)


Recommended Practice
Rationale

TSS target and filter rating detennined by


particle characterization; estimated levels <
30 ppm for TSS and < 25 J.I absolute for
filter size

beds preferred to cartridge units where


possible

Carbell

with the exception of "deep bed" systems


coaIlmed c.aroon prefmed over wood based
carl>on
additional mechanical filtration downstream
of carbon system with < 5 f.l absolute I'llting
(see paniculare removal)

cartridge unit have shorter life, requiring


more frequent change:out and thus less
likelihood oftJeing changed out when
required
coal based carbon has bigher adsorption
capacity. broader distribution of micro pore
sizes and is harder than wood based carbon
several facilities with no filtration
downsttcam of caJbon unit reponed problems
with caJbon. fines in amine

caJbon perfonnance is very sensitive to


loading procedures
full flow lean filtration is already
recommended in "Amine Treating Best
Operating Practices" and is commonly
used in Chevron facilities
determination of appropriate TSS targets
and filter raring requires particle
characterization (see notes)
TSS targets of 30 ppm and filter rating of
25 J.I absolute were typic:a1 of upstream gas
plants which have more stringent
requirements

dual filtration system with full flow filtration


on lean lor rich) upstream of earbon units and
slip stre:llTl filtration downstream of carbon
unit; slip stream rate determined by carbon
treatment requirements
csrimale 25 f.l and 5 ",.absolute filter raring
on fuUliow and slip stream filters
rcspecri"ely (again depends on particle
c:baraderization)
TSS larJ;:et < 30 ppm

duaJ filtration recommended by vendors; full


flow filler achieves bulk removal, slip
stream filtration removes fiDes this
arrangement minimizes capital costs

APPENDIX
SURVEY DATA

Survey Data Overview


A. Upstream Facilities:
CCR - Kaybob South, Bigoray, West Pembina, Medicine Lodge, Mitsue
CUSA - Carter Creek
Warren - Sandhills #193, Leedey#217, Sulphur Springs (Como), Monohan (Wickett), Sanders,
Canadian

TI~e

Of Amine Plant

Number Of Plants

DEA
MDEA
UCARSOL
MEA
Total

Volume Of Gas
Treated (MMSCFD}

5
2

597
70
34
146

12

847

Total Amine
Circulation
(GPM}
9290
45
85
1190
10610

3 non-associated gas plants


9 solution gas plants

B. Downstream Facilities:
CUSA Products - Richmond #5
Pascagoula (all plants combined on one survey form)
EI Paso Areas 2 & 5
EI Segundo Plants 2,4,&5
Salt Lake City
Hawaii

TI~e

Of Amine Plant

Number Of Plants

DEA
MDEA
MEA
Total

Volume Of Gas
Treated (MMSCFD)

5
2

125
29
27
181

Total Amine
Circulation
(GPM)
7200
285
320

7805

C. What Constitutes Good Performance:


Use number of incidents of off spec gas per volume gas throughput or per volume amine
circulated as guide. Note that for upstream facilities off spec gas generally means> 4 ppm
whereas for downstream facilities off spec gas means - > 50 ppm
U~stream

Total Gas (MMSCFD)


Average Gas (MMSCFD)
Total Amine (GPM)
Average Amine (GPM)
Total Incidents Per Year
Average Incidents Per Year
Incidents Per E4 MMSCF
Incidents Per E8 Gallons

847
70
10610
884

174
14.5
5.6
3.1

Downstream
181

20
7800
870
64
7
9.7
1.7

Operational/Design
Issue

SUMMARY OF K.t. V SURVEY DATA


Upstream Facilities - Observation

Downstream Facilities - Observations

Free Hydrocarbon
Removal
(skimming I inlet
scrubbing)

of the plants with the four highest incident rates all are solution gas plants, however the
majority of the plants are" solution gas plants
of the 4 worst upstream performers 2 do not have skimming systems and one has a system
which is rarely used
of the remaining 8 plants all have skimming systems except for two, one of which
processes dry gas
some plants have skimming systems in multiple locations and these are generally better
perfonners
most common location for skimming system is on flash drum but also have systems on
contactor, regenerator reflux drum, and surge tank
all, systems are manually controlled
all plants have inlet separators or knockout scrubbers
2 out of 12 plants have inlet coalescors as well as inlet separators
one plant has recently ( I year ago) taken coalesor filter out of service with no noticeable
impact

all plants have skimming systems, most commonly on flash drum but also occurs on
regenerator, contactor and surge tank
3 plants have skim systems on multiple locations
no clear correlation between skim systems and performance
all systems are manually controlled
all plants have knockout scrubbers
no plants have inlet coalescors

Entrained
Dissolved
Hydrocarbon
Removal (carbon)

all plants have carbon systems although one is out of service; 7 out of 12 are beds, 2 are
cartridge systems arid one is combined with particulate filtration
10 out of 12 carbon systems are located on lean amine downstream of particulate filters, the
two units located on the rich side do not report any apparent advantages and in fact are two
of the four plants which have incidents rates> 15 per year
all carbon treatment is on slip streams ranging from 5 to 30% of total flow, average - 20%
excluding one plant the minimum frequency of carbon changeout is semi-annual, many
changeout more frequently on basis of problems or amine quality, one plant changes out
every two years with no reported problems
only lout of 12 facilities uses steam regeneration; others have used it but report that is had
minimal value and could upset the bed
3 of 12 plants have additional filtration downstream of carbon beds
3 plants report foaming problems due to carbon fines occasionally breaking out of beds

2 plants have inlet water wash systems


out of9 plants only 2 have permanent carbon systems in operation, one plant has taken
it's system out of service, 3 plants have used / are using temporary carbon systems on as
needed basis, 3 plants have no carbon systems at all
where carbon systems (permanent & temporary) are in place slip stream rates range from
I to 25% offull flow with an average of -12%
minimum frequency of carbon changeout is annual
where carbon systems (permanent & temporary) are in place, 80% have both upstream
and downstream filtration

Particulate
Removal
(filtration)

all plants have cartridge filters on lean amine although one plant no longer uses the filter
5 out of9 plants filter full flow, the remaining plants filter slipstreams ranging from 10
to 50%, averaging -20%
micron rating of filters ranges from 3 to 40 microns with an average of20 microns
plants without carbon tend to have higher micron ratings
only two plants monitor TSS routinely and target <200 PPM

General

all plants have particulate filtration


5 out of 12 plants filter just lean, 3 plants filter both rich and lean and 4 plants filter rich
only - filtration on rich side not correlated with good performance, in fact the four worst
performers all filter on rich
3 plants have dual filtration systems with second filter having finer micron rating and
installed on slip stream flow through carbon system
9 out of 12 plants have at least I filter system designed for full flow filtration, 3 plants filter
< I 5% sl ipstreams
of9 full flow systems 3 are cartridge units, 5 are bag systems and I is a sock filter
of 6 slip stream systems I is a leaf filter, I is a cartridge, 3 are bag systems and I is a sock
minimum micron rating of all systems (including dual filtration systems) ranges from 3 to
50 microns with an average of -25 microns
where there are dual systems the full flow filter is rated at 20 - 25 microns and the "
slipstream filter is rated at 5 microns
most plants that monitor TSS target for <25 PPM
average contactor operating pressure - 860 PSI, minimum - 600 PSI
average HSS - 0.7% of amine
SRU upsets due to carry over from amine plant not considered a problem

average contactor operating pressure - 120 PSI; maximum - 200 PSI


average HSS - 8.1 % of amine
with the exception of one plant SRU upsets due to carry over from the amine plant are
not considered a problem

Amine Filtration & Hydl"Ocarbon Removal Best Practice - Survey Data Summary
Sheet 1 - Gene.-allnfOlmation

r"arneorFacilily

WestPembm.a

MedicineLodp:e

OpeUling Comp.lny

Coal.lcl PenOD

Telepbone

0"

Type or

Type or

Facllll),

AmiDe

Volume or

Temp. or

Cas Treated
Gas
(MMSCFD) Treated

J'ressure
OrCas
Treated
(psi&)

H2S
COllleat

(Mol'"!.)

CO2
Coateat
(Mol-I_)

CI Coaicli Cl CoaieD.
(Mo'''.)
(Mol-/e)

CCR

Hendemm. l"lclci

403-622-6042

403-6226006

Gal Planl

DEA

40<>

"

'"

12.2

2.2

71.7

CCR

GBno.B~

4038942103

403-8942109

Gas Plant

MOEA

"

97

1000

0.05

0.66

"

34

"

CCR

RonMehn

4038943611

4038943973

au Plant

Ucanol

1.5

Source or
TrMlledG:n

Type or

Liquid
Trelited

Volume or

Number or

Liquid
Treated
(BPOD)

EvcIIlIOfOfl
Spec Sweet
Gas Per Yell

FrrqH1lCYOf

iatldcabl
EI2SCF

(addoaul
E9pl

CCR

Davo Hutchi.Jon

4037942106

403-7943959

Gat Plan!

DEA

15

'"

'.3

4.2

84

1.5

BillJen.Icins

403-849.7934

403-8497989

GuPlan!

MDEA

"

600

0.02

0.58

"

40

"~lIaaC)'or

AmiDe eire.
("I. ar Ma.

AIItJ.."oa. Use
(COIIUliliou/u

C.~cily)

........

NonA$SoCUIted.
GuProduction

54.79

2.54

aeeded)

Solutionps
Droduction

1.56.56

253.68

30

2417.41

671.50

730.59

34.59

20

1565.56

1268.39

..."

82.19

9.36

FouledRiboilOl1l

761.04

amine foaming J HC
contunin.a.tion

PI dow, inadequate

production

CCR

Amiae
eire.
(GPM)

y...)

Solutionflllll

1000

CallH:SOrorrspeeGIIS SRUaptet.due
(Imlae fCllmta. He
to .mlae any
cO.. t.ml ..atloD, oLber) over (lima per

NonAnoc:iated
Qu Production

So.IUtiOllgBS

1lf.>duclion

LPG Mix

NonAJsoc:ia(ed

Inlet

9.93

au !"roducbon

condensate

8.7

NonAssociated
Go Production

1350

"

0.3

40

0.3

VUlQINF

u needed

COITOf,IOD

I,,"'bltor
T,...

Petromeom
WSs8

UnionC~

amine foaming due to He


cont:amirultion
amine foaming due to H
contaminatitm

"

.Il",

"

70

220

70

30

10

"
"

0.1

LB 1215

contmUOWl

Vanol

uneeded

TraviJAFI

u ......

"

0.7

v....

1.8

SarfonicN10
(CoutaI)

u...w

Com:it7669

u~

umon
c.rlrido

SandhillJIH93

w"'"

~/:I217

Don Hallam

AaAlbriltlll

915-563-0822

405-488-3850

915558-2012

40~-4882968

Gu Plan!

QuPlant

MEA

DEA

700

100

"

100

1000

2.51

0.0005

1.98

0.9

76.23

84

833

LPChnDt

20

1304.63

610

"

28

"

100

"
20

0.4

O.IM

NatunalGu
SulphUfSp~

JohnDunl:l

903-488-3211

903-488-3058

Gas Plan!

MEA

37S

"

16'

16

Wickett Plant

R. F.On.y

CI"N33S-6280

CTN-33S-6281

Gas Plant

MEA

833

100

150

0.12

SaundenPlanl

IR.Bovd

505396-3221

50S396-7702

Gal Plant

MEA

"

76

810

806-3239710

Ou Plant

DEA

S15

88

OUPlant

DEA

CIlhIId1anPw.1

w"'"

lIIlrich E. S~

806-323-8020

CutcrCreeIr:

CUSA-Production

~W.to1rich

CTN783-4596

0.457

0.6

14.4

UOPAmine

"

14.5

Production

14.61

RIL Hx Tube Leab

.00

"

80.738

18.685

N"""'Gu
Production

9.87

Pump

"

40

92.331

2.671

322.32

I"

80

17.5

70

23'46

20

"

27

89

27

4000

9'

10

228.31

63'

3000

Subtotal UPttrnm

2831

174

168.39

11.20

10610

Averue Upstream

23S.92

14.50

168.39

31.20

150.53

4.37

438.36

1.77

483.48

28.54

NA

NA

"

1133.68

50.74

0.00

0.00

Richmond NS H2S

CUSA"""""

JCuenRooker

510-242-1547

510-2421542

Refinerv

700

120

4.75

"

85

DEA

22

AmineGuan
ST

0.00

0.7

CloudST

..........
Af7669

uMedied

14301ll1icclae
SAG<3Iyo1
...

u ......

Betz:f'C629

COIltiaaous

BmWSS8

0.S4

884.11

m.dequabl DEA

LPO

10000

cin:ulation

870

92

28

Niko 5757

u Deeded

66

30

00.-810

u..ted

85

"

Cobr,f'CC,

.~

PUC&flouia(all planlJ)

aJSAProduclJ

ElPuoArn5

CUSA"""""

1imKen

El Paso Area 2

CUSA"""""

Kriltie Drelik

CUSA-"""""
EISep:undo1l5

JemnyOn.fton

601938-4S67

~finery

DEI!.

crn775550s

crn77S3368

Refinery

MDEA

CTN-nS3291

CTN-775-3251

RefinerY

DEI!.

601938-4S59

17

c:nuIeunit

90-115

100

90-100

100~130

andeanil

Paul Bnullov

CTN-640-5114

CTN-640-5179

~Iinery

DEI!.

'9

90

120

7.'

Sieve Leichly

CTN-640-5629

CTN-640-5233

Re~ery

MEl!.

12

110

190

0.9

0.9

CUSA"""""

Tin Yin Lam

CI'N-640-57IS

CTN-640-5920

ReliDery

DEI!.

"

100

100

12

80

"

3.3

0.9]

"

210

130

CUSA-"""""

Jason Lehfeld

808-682-2276

808-682-2361

Refinav

MEA

181,4

n."

LPG,D,C4

9000

N...

CUSA ProduCtl

aJS.A - Produca

SlIbtor..1 DoWIIStrnnil

".

1500

"

27

"

FCC
(:obr,
hydratraten,

C3

'000

f:lVdennit

LPGmix

2400

0.00

0.00

71.6

Hydrotlnten,
crndc 1lDit

LPG mix

4200

42

9589.04

940.10

67

FCC, aude unit

LPG mix

8300

0.00

0.00

...~I

16.47

886.06

16.47

7.33

200

1'5-100

20

_ ....... n'"
0.3

450

77

23

0.'

230

66

"
"
"
"

7.'

1400
85

NA

90

1.1'

147n

os

........
N.
N.

5-10

IiIK:onbued

uDMded

4.'

N1ko71D5

uDMded

u .......

N.

20

N.

Polvnlfide

N.

7.41

6111196

Amine Filtration & Hydrocarbon Removal Best Practice - Survey Data Summary
Sheet 2 - Hydrocarbon Removal - General & Skimming

Name Of Facility

Type Of Organic I HC
Contamination

Frequency Of
Contamination

IType v. uperanon

Kaybob South

Dissolved HC

Infrequent

Skimming

Free oil

Infrequent

West Pembina

Free oil &:. eJltrained H~_

frequent upset

Skimmin~

ISkimming&:.

CaatrolOf
Skimming
. System

c~:;t;:fi~:

Manual

, ~en. &:. thus amine loss

oontactor

Manual

out carbon filter on PM basis

IIash tank

manual

Rule. Of Tbumb

HC,
BiI!oray

Lacatlon(S) Of
Sldmmln~ Systems

Lcauses .<hnrt fil ..... hr.

foaming in

IMaintain temp. difference of 12 - 18 F between , &:. amine


maintain .
temp between 85 & 100 F; lO%
10 oomnn' m;n;m;,. use of anti-foam by controlling inlet gas
Medicine Lodge

Dissolved HC

Infrequent

Mitsue

Dissolved I entrained HC &:.


residual corrosion inhibitor

Frequent

Carbon

none.

Coalescing filter &:. I~ carbon filters every I - 2 months; maintain temp.


carbon
ldifferential

none

Iln...1I ."".hh.... on contactor overhead &:. have it dump 10

Sandhills #193

Dissolved I entrained HC &:.


residual corrosion inhibitor
,,~.,

Leedey #217

n;1 n. ltr

amine I.
. Amine then Dows to IIash tank. HC
from .
is treated on side stream amine &:. used as
. Maintain tem!>. differential

e.'

Frequent

S~&:.carbon

Infrequent

Dissolved or

~ ...

Iltr

Saunders Plant

Free oilorHC

Infrequent

Canadian Plant

Dissolved or entrained HC

Continuous
treatment concern

Carter Creek

Dissolved I entrained HC &:.


I corrosion inhibitor

Continuous
treatment concern

Free
Riclunond #5 H2S
Pascagoula (all plants)
EI Paso Area 5
EI Paso Area 2
El Segundo #4
EI Segundo #2
El Segundo #5
Salt Lake City
Hawaii

e~~~~OIVed or
Free oil or HC
Entrained HC
Free oil
Free oil or HC
Free oil
oil or HC I Dissolved or
entrained HC

Dissolved or entrained HC
Free oil or HC

Infrequent

Infi:equent
Infrequent
Infrequent

none
SUnletank

Manual

none

liJtering

Flash tank

Manual

Skimmin~ &:. carbon

Contaclor, Dash tank

Manual

Flash tank, regeJlerator

Manual

Flash tank

Manual

Flash tank
Flash tank
Flash tank, absorber
Absorber

Manual
Manual
Manual
Manual

Ie.'

,carbon
Skimming

Continuous

Frequent
Frequent
Infrequent
. Infrequent

leales. No data

Activated Carbon 'given.


Activated Carbon
Activated Carbon,
Sock filters
/fwe push to 34 MMSCFD we tend to raise the Dp accross
Ithe 22 tray lower to near 80" w.c. 54"IDx6I'-Q" SIS
particulate
Activated
carboniCoalesor

Infrequent

Manual

none

!Cun'ently out of service due to


Sulphur Springs
Wickett Plant.

IIash tank, surge tank

IRemove as much free oil as

ISkimmin~

IS~&:.carbon
Skimming
maintain differential temperature
SIimrning
have used temporary activated charcoal
Skimming
,stream 10 oomnn .Irim regenerator I absorber
' I..,pl shows HC > 6"
ISkimming&:'

Ie.

,carbon
Skimming

Swgc':":~;rber,
Absorber
Surge tank

Manual
Manual
Manual

6/11/96

Amine Filtration & Hydrocarbon Removal Best Practice - Survey Data Summary
Sheet 3 - Hydrocarbon Removal - Activated Carbon & Feed Pretreatment
~Ior

N.... or r.dllf:\

""".... or

T,'..., orl:nI.

enhon l:1II1

Siuor
Clnon

e ..... Ml'If

a.lrer (L8)

su...

F~'

at

10

Crtmi_ for

o.annoul

ChaAac:doul
with
puticul.1e
filler

CombilKd
"ith
KI"bob South

...........
l!...,-n_'

n- T..
e.rhoa l 'IBI

Chanl!ftlQt

Filtninll!

DP Ii. Imine
uolir.-

10 boldin, pits A then


buried

5CCpllniculllcfillerin
No -

Lean jusl before:


retunllnllo

Bi

carbon bed

0111\

WcslPr:mbi ...

McdicineLodllc

nrbonbcd

luction

carbon bed Lean. after cooler

"

10

30

100

10

.00

Monthh'
E"cl'\' 3 dl\"s

DP

No

HaunIoID
fllCilin'

-.cd 10 . ,

partinl.lc tillcn

"*aor fillet hal

upsllam _ nothinl

mno\-cd il "idl ..

downslrcam

irnpKl

,.ute disposa

uartel'h'

partKulllcfililm
up3tn:am II:

IlIleI"",

do\\'nsuam

coaiaot'tiller

follcm-.l ~.

c.nbir..aI

"

.....

,antidc

MibllC

Sutdhilb =19.1

SulehurSorin s

partic.Jltc (iI~
upstn:ua.lIOlkin.

Rich-bcmftftflash
a:. re en.

10

lank

Caniuel' bulk Lean before amine


~pe
Ill!fiC
Le.n-inldle

I - 2 rnonlhs

1350

h.IO.6lC10
B:'I[ 10
scmi.,.nWLI

foamin.

No

cliff_ .. iaJ.t
scpaDM' A.

N.

downstream

upstream.,.,tiltcr
(25micronJ.
m'ftltrDam lOCk (5
Upon r_inr

No

Wuhabun

d.aih~lor

",~ron)

InI01~1On

DP

"

None

U~n

No

No

aofilnaboft

"

I.'"

6:dO

_i-Innual

_ilofl.MiftC
q .... ir,.
monilGrin,

~2S
stJamsoct filter

No

............

(dm\lntlnachcd

BIIt\on silC

Inldba.scRibber

--

No

Jb\'chorizoaIaI

,..... ~ fn.lo(

,lUll (i. . . .,o\. . .


_ _lLD\at..!

OI:~um:nc.or

........mi .. lOCt
fillc,. upsuam or
c:hucoaJ. CMIlfC

opcRItilll
ptObkrns. bail

Saund~nPfanl

LcaIHlo\\lIItream
\'crll~al \'C!L'lC1 ICln sock fill~n

CAe 150.
H(7S GPM)

6SOO

~~~

olke C\.~.

or..mftCqualir,.
monuonnl.
~olo,

GAGS

IUnu

!'Cll1I

fillcn"lwnDp~7

No

i ..lcmaIlCl'IIIbbcr.
lOp of IU eo.trKloi
to ~lIccl CWf!o'O''CI',

I"rf1I..aIco _ _

nah ,ascI.

On lanlille

KOCH-LlQ
.~"drucarbon Imu'le
s.ixcrinlinarorliq

trabnl.

KinllDOl coUaor
lilter. Uailp

RKhlncrnub
c.-Jiu Planl

~arbon

beds and bal!

fill~r

\.ria G-100

1700

IUO

_i .. nul

O:lIfftIICcof
opc,.lInl
robkms

...._ o f

dU.c: ..... lin (an.

No

hilhc:orrosi~

CartcrCrect

Lan before sU'le


urbon beds link

7000

6:oc 10

_i'lnnWlI

iMibilor
l'Oidlllll

Icmpo,wr

,......

..... CO . . . . . . . .,..
,topped

lalllGrelcecnboR
faeilin'

,,_tl~T3rS..

abtorbance. lurbidin'

~S

Pesn.llull'llI

IllS
'1IIbi

tcrnpol1l~'
loCIfI - do,,'ftSlRun
clrbonbcds ofplnic:ulltc fillCI'I

noC:lrbon

IS OIII~
when ncCIXd

10000

N.

upIolRl ....ltdbq

lihers dowmnan.

facililiesonh' -...rKe

none
Lcan.II\crrich

Coa~ filler

~.""dJe fillcn

foamillior

Richmond

upslrelm partieullte

No

N.

N.

N.

lupslRlm ".rticYiaIe No

N.

_.,,1w:a
Innual

No

EIPuoAreal

.......

None ....nl
1~!IIpOfII~

FJ Sc ulld..

~"

No

basiS

"....,,,'Dh.
poI~'HIpfMc

ICnbbcr. ialel

F.I Sc:IIUndn

EI Selunda

~l

=~

N.~

Carboll bedslem"",.. r;. L.c.n - downstream


IKI/IIIC::!
of rich lean
11I5talled
c:occhanllen

'"

2000

8~.lO

Innual

_.r

kftoctOlddntM

No

InJcltnoctOUll

No

Upsll'CMl
~rt;culalC.

amine

RelumlDCaI.OII

""cd:"',

'I''''

~a.rbon

Upsl_malll
~rtlf;;u.I.lcfih~r:

Sail Lakc{;ln

Lan dol\'ftSU'eam
Carbon beds of .mine coolc'

dO\\ns~

160<1

11'1.10

IMUIII

5ma11er IlIlel tnoctOUl tt.


artlculalc/illen
wIlCt'wash

N.

catbonbed hit... nol been

N.

.1Id.mallcl
do\\n.lIn: ....

o[lCincoolcr

1<,

IIS0

N~,

urban

loc.u:
InlelKrubber

N.

6/11/96

Amine Filtration & Hydrocarbon Removal Best Practice - Survey Data Snnunary
Sheet 4 - Particulate Removal

N... or:r.riitT

K.

Tn.Oni!:

1.<.

obScll:b.

MIlk,OfFill"

~~~.

F\h:.,.laflti

.""'

..........

_01 Criwjo'no

or"'w

14~

"

"

'"

"

100

100

100

100

"""
coolabd'onda.lqe

l'or_Mr.u

Wn:rPCIIIbma

GAl'

Wa.8:eI'lI.u!atllllr.

BoIbOll._. . b..
dowu!r.aol

-pwIfI-"

a Mdt (10
UI~Lo4lre

,-

B.. PtlcockSodt :"urboiI.&a.GlltotI

Rdr,

......

D_ ....

S...... I!n

....

nc-"61

.so-__

"

,--

-- ...w_-.
.""""

"

B.. 5 Sock

"

10-..

100

B.. (2'

,--

B -Ro.. .we

lire.

C _ " C..... Ool,B..


".
B

""'.-

at.,..

1>0

~Lo
. '_
brfol'tc-.aOl'

=..sM.

"

S.t.2S

A61itMc_ TSS

~;

..

IJ~.

C_.
1000

B.. 25.
C

100

"'N_

."

v_

R... orn-ll,.

N.

N.

------.
:::eo=:-PPN

~c-=n._

-_.

...."". -.--~."p- ... w.t. _ _ . . . . . .

--

..........
...,...
......

.,

B.. 100,
C

.aM.,

~M_.

!N..w,.TSS'

DP

Ih.. -~.j.

eac'

C. . . . I

_r.nUl

...........

c 100PP

BSS

c~_

BItDP.

..)a..odI SodlW..ao.JU,

ltdI,.b.. lilk6uh

.",

'"

-"
-

.,-

BSS

DP

1bra.10IM

to,

(8PP1l). TSSIk&t:rC25PPN)IloIIW)'-C.. 14
CaC03. 0., F..... N.. 'IlMNpIIP. NetI&t. FGrIIIi= Aad.

~-

10 ......

_'Oclr.~l_

B.. (5-=raa)

.nide.

WtSlJ- dIknin: (JOOfPJ,l). . . . . . . . (70 PPw III B2S).

DP

.........

1Ih_lourtloalilla

..... """' .......

~.-.

......

20.,,_

_.
..........

IA.c_.~l.'ISSCI\C.pPII(15n),l)TSSbeCon . .

...... DP:

Le... . . . u'l106
1JSFber

""

.aa.koRl!l',.....t.

Lo.

'_01
"-T,nt:

do.

_ _ 5_.-.a .......

.....

c l - - . ....

D .... ,""

-.:...u.., .... _ b t

l.d,b_C,oI
.~

Po_....

W.-.WnIdJ'.

110

"

Ie.

._

DP

.--

GM.2mlOdr:
__

~_il

~ _o..

W..atnlFollCl'

W,clllltl'l.-

,...... "'"
C_"'"

-- -_

.....,......

BJ'I''''._'.

WqUnaF~

StOG .....d

C..",Cretk

P.II_'''II'U~

"*.....

..

. . . IIOdr._

I~":-

C~

,.

...t.ola .,...,......,

'"

'"
17~

..

lA ... C... dlll


ANfCVNODIY

Fls ........ n

C........

ChI"llOllS u:uI

.El.S-OO~

C......

COtlD'ol~

kJr,.5Q.&o
lA... 4J

10

100

,0-'"

'"
"

20~.IOO

102' .....

lA .. ___ oI
ncb'~

..... _.

I~-:'

1'/.0

2C:-

'"

l2-j

10.

..

"

'"

18~

.,

17

I~:-

loj~

,.

t..1II_1II

...Lo._._"
,"-

c~

100

"".--~

ElPu.Arra2

C....,

DP

las .. f ....... I0 . . . . ~

aa8~lA.

1!.oM.o.

Lc... do-._o

E1S~"

"-

RIch . . . . . . .
a.llllllk...lA.____.LP

F~.

ElPuoAn.~

"'N_

C..- ..... -..ac..,..., ...

.,. dowuln_

'M

100

. . . . . . r--.pKb4 ......
~1I_LPO ..... 1.2.(j".

Lo.

R2S

'"

20
I~

"
"
2~.-..I

2' ......

......

._-u_

--

12 .....

,_

......

.....

DP

.. NDIL\I"' .. _

DP

I:.TSS(CIOpp.i......-.(CINN).~(C'

....

'.1--.

DP

D'

'.10_

..1\1...... &1""

!--- .....,.. ..IqIIIK7'.I'DP

D'

~TSS""P""

_,TSS_",,_pp

DP

No

-_
N.

D.

DP.t.,...

'"'"

N.

D'
DP

..... - . . . . . . 2 . . . . . . .
N.

N_

..

.N_

Lc... do _ _ taol:
Sat: I.IIr.. Wr7

C........

FslMiaolillOf

1-::-

It.. _eoolll'f

'"

10.,,-...

2 .......

DP

Lcaado_taof

""""

C.......

CI,TNO

Inn_eeool,,"

1I'lo

"

N .....

6111198