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SECTION 21

Hydrocarbon Treating
There are many methods that may be employed to remove each of these techniques are described and a general bibliogra-
acidic components (primarily H2S and CO2) and other impuri- phy for additional reading is included. Because of the diversity
ties from hydrocarbon streams. The available methods may be of the processes available, and new processes being introduced,
broadly categorized as those depending on chemical reaction, all possible processes are not discussed. Note that gas treating
absorption, adsorption or permeation. Processes employing generally implies the removal of contaminants, while gas pro-
cessing normally refers to the recovery of NGLs.

DEFINITIONS OF WORDS AND Heat Stable Salts: Ionic contaminants that do not allow the
amine to be fully regenerated.
PHRASES USED IN HYDROCARBON
TREATING Mercaptan: Any of a homologous series of organosulfur com-
pounds, known as thiols that contain a sulfur-hydrogen bond
Absorption: A separation process involving the transfer of a (S-H). Thiols are the sulfur analogues of alcohols of the gen-
substance from a gaseous phase to a liquid phase through the eral formula RSH where the “R” represents the alkyl group
phase boundary. that the S-H group is attached to as it would be attached to the
O-H group of the corresponding alcohol. All of these materials
Acid gas: Often used in reference to the concentrated H2S/CO2
stream coming from an AGR unit. possess a foul odor, e.g., methyl mercaptan.

Acid gases: Impurities in a gas stream usually consisting of CO 2, Organic Sulfur: Includes COS, CS2, and mercaptans.
H2S, COS, RSH, and occasionally SO2. Most common in natu- Physical solvent: A liquid capable of absorbing selected gas
ral gas are CO2 and H2S. components by solubility alone without associated chemical
reactions.
AGE: Acid Gas Enrichment
AGR/AGRU: Acid Gas Removal / Acid Gas Removal Unit ppmv: A volumetric concentration of a species in a bulk fluid
measured in parts per million.
Acid gas loading: The amount of acid gas, on a molar or volu-
Residence time: The time period for which a fluid will be con-
metric basis, that will be picked up by a solvent.
tained within a specified volume.
Adsorption: The process by which gaseous components adhere
Selective treating: Preferential removal of one acid gas compo-
to solids because of their molecular attraction to the solid
surface. nent (usually H2S), leaving at least some of the other acid gas
components in the treated stream.
Alkanolamine: An organic nitrogen containing compound re-
Sour gas: Natural gas containing undesirable quantities of hy-
lated to ammonia having at least one, if not two or three linear
or branched alkanol groups where only one or two could also drogen sulfide, other sulfur species (such as mercaptans or
COS) and/or carbon dioxide.
be substituted with a linear or branched alkyl group (e.g., as
in methyldiethanolamine, or “MDEA”). The number of hydro- SWS: Sour water stripper.
gen atoms substituted by alkanol or alkyl groups at the amino
site determine whether the alkanolamine is primary, second- Sterically hindered amine: An alkanolamine containing a
ary or tertiary. bulky substituent group close to the amino nitrogen to lower
the stability of the carbamate ion thus inhibiting reactions
Antifoam: A substance added to the treating system to reduce with CO2 directly with the amine, e.g., DIPA (diisopropanol-
the tendency for the solvent to foam. amine), AMP (2-Amino-2-methyl-1-propanol), or FLEXSORB®SE.
Chelate: An organic molecule in which a central metallic ion is SRU: Sulfur recovery unit.
held in a coordination compound.
Sweet gas: Gas which has no more than the maximum sulfur
Claus process: The process in which one third of the H2S is content defined by: (1) the specifications for the sales gas from
burned to SO2 which is then reacted with the remaining H2S a plant; (2) the definition by a legal body such as the Texas
to produce elemental sulfur. Railroad Commission.
Degradation products: Impurities in a treating solution that TGCU (tail gas clean-up unit): a process unit that takes tail
are formed from both reversible and irreversible side gas from a SRU and recovers additional sulfur .
reactions.
Threshold limit value (TLV): The amount of a contaminant to
Doctor sweet: Describes a hydrocarbon stream which has had which a person can have repeated exposure for an eight hour
mercaptans removed to a level that it passes the Doctor Test day without adverse effects.
(GPA-1138).
Grain: A unit of mass where one pound is equivalent to 7,000
grains and a specification of 0.25 grain of H 2S per 100 SCF is
equivalent to an H2S concentration of 4.0 ppmv.

21-1
SAFETY PRECAUTIONS Removal of these contaminants from hydrocarbon streams
is required for reasons of safety, corrosion control, gas and/or
Hydrogen sulfide is a highly toxic gas. At concentrations as liquid product specifications, to prevent freeze-out at low tem-
low as 10 ppmv irritation of the eyes, nose, and throat is possi- peratures, to decrease compression costs, to prevent poisoning
ble. The human nose can detect hydrogen sulfide in concentra- of catalysts in downstream facilities and to meet environmental
tions as low as 0.02 ppmv. However, the human sense of smell requirements. The removal of water (dehydration) is discussed
cannot be relied on to detect hazardous concentrations of hydro- in Section 20, while nitrogen rejection and the combined NGL
gen sulfide. Higher concentrations and extended exposure to recovery/carbon dioxide removal (Ryan/Holmes) process is cov-
hydrogen sulfide will desensitize the sense of smell. The concen- ered in Section 16. The discussion in this section will deal with
trations inducing different reactions by the human body are:1 removal of some or all of the sulfur-containing compounds and
 Threshold limit value (TLV) for prolonged exposure: 10 carbon dioxide and heavy hydrocarbon, mercury, and oxygen
ppmv removal.
 Slight symptoms after several hours exposure: 10–100 Ammonia (NH3) and hydrogen cyanide (HCN) may occur in
ppmv other facilities (e.g., refineries), but rarely in gas treating
 Maximum concentration that can be inhaled for one hour plants. Consequently, they are not discussed here. Arsenic
without serious effects such as significant eye and respi- (primarily as arsine) has rarely been encountered, and is not
ratory irritation: 200–300 ppmv covered here. SO2 may occur in flue gas. However, flue gas
cleanup is outside the scope of this discussion.
 Dangerous after exposure of 30 minutes to one hour:
500–700 ppmv
GAS PRETREATMENT
 Fatal in less than 30 minutes: 700–900 ppmv and above.
 Death in minutes: greater than 1000 ppmv All gas sweetening units should have well-designed pre-
treatment facilities. Carryover of brine or liquid hydrocarbon
Hydrogen sulfide is highly flammable and will combust in (as slugs or aerosol) from upstream production operations can
air at concentrations from 4.3 to 46.0 volume percent. Hydrogen cause problems for gas treating and downstream processing
sulfide is heavier than air and may migrate considerable dis- equipment. Also, field facilities are not typically designed to re-
tances to a source of ignition. move troublesome contaminants like gas-phase heavy hydro-
carbons. These contaminants can likewise cause operational
Carbon dioxide is a naturally occurring gas that is 50%
difficulties in the sweetening process.
heavier than air and is colorless and odorless. It is a principal
by-product of combustion of hydrocarbons. CO2 is inert and Inlet Separation
therefore non-flammable. CO2 will displace oxygen and can cre-
ate an oxygen-deficient atmosphere, potentially resulting in If gross liquid carryover from an upstream facility is possi-
suffocation. The principal hazard of CO2 is exposure to elevated ble, a slug catcher is recommended. It should be sized not only
concentrations. The atmospheric concentration immediately for steady inlet fluid volumes, but for surge capacity to handle
hazardous to life is 10% (volume).2 Because CO2 is heavier than slugs of liquid hydrocarbons, water, and/or well treatment
air, its hazard potential is increased, especially when entering chemicals. See Section 17 for options regarding slug catcher
tanks and vessels. “A common but erroneous belief is that CO2 design.
simply acts as an asphyxiant by lowering the oxygen level be-
low the 16 percent minimum necessary to sustain life (at sea If aerosols are a concern, an inlet filter separator is sug-
level). Although this is frequently the case in most serious ac- gested. Selected filter elements if combined with properly de-
cidents, CO2 begins to have a noticeable effect on normal body signed coalescing devices can remove entrained droplets down
functions at about two to three percent. The concentration of to 0.3 microns in diameter. The detailed design of filter separa-
carbon dioxide in the blood affects the rate of breathing, a mea- tors is described in Section 7. Note that the effectiveness of a
surable increase resulting from a level of one percent in the in- filter separator may be enhanced by the injection of a small
spired air.”2 amount of polymer into the gas stream upstream of the filter.3

Anyone engaged in the design or operation of a facility in which Water Wash


H2S and/or CO2 are present should seek expert advice for detailed In lieu of an inlet filter separator, a water wash column as
safety precautions and mechanical design considerations. shown in Fig. 21-1 may be placed ahead of the sweetening unit.
Water washing can be particularly effective for removing glycol
POSSIBLE CONTAMINANTS or methanol mists or fogs as well as reducing the vapor phase
Ammonia (NH3) concentration of those contaminants. Of course, stainless steel
Hydrogen sulfide (H2S) or other corrosion-resistant alloy should be considered for water
Hydrogen cyanide (HCN) washing in a sour environment. Trays can be sieve type, valve
Carbon dioxide (CO2) type, or other design as recommended by a vendor. Most of the
Carbonyl sulfide (COS) time weirs are 2.5 to 3 inches high, and a reasonable pressure
Disulfides (DMS CS2) differential for the gas stream is 1.5 psi. A demister pad is rec-
Mercaptans (RSH) ommended at the gas outlet.
Nitrogen (N2) Water circulation rate should be 1 gallon per each 5 to 7 Mscf
Water (H2O) of gas (or 10 GPM per 80 to 100 MMscfd of gas). The recom-
Sulfur dioxide (SO2) mended make up rate is 2 to 3% of the circulation, but this figure
Elemental sulfur can be changed based on analytical results. The source of make
Elemental and organic mercury (Hg) up water can be stripped sour water, if available in the plant.
Arsenic
Oxygen

21-2
FIG. 21-1
Typical Water Wash Schematic

Rich Amine

Stripped Sour Water Make-up


Sour
Gas

Purge to SWS

A white paper developed by members of GPA’s Technical first step is to try to find and correct the source of oxygen entry
Section A (Facilities Design), titled, “Design Considerations for into the system. This is often the simplest and most cost effec-
Water Wash Installations,” may be obtained from GPA for a tive approach. Most oxygen leaks may be traced to compressor
more in depth description of this system and possible design suctions or pipe fittings.
alternatives.
To eliminate oxygen contamination a number of possibilities
In the case of fine iron sulfide blowing in a dry pipeline, a exist:
glycol wash column has been reported to be an effective means
of solids removal.4 React the oxygen with chemicals.

For liquid hydrocarbon treatment, a filter coalescer may be  Chemicals such as amines, organics or inorganic com-
used to remove suspended water or glycol prior to further pounds may be added to remove free oxygen. Oxygen
processing. scavengers are available from many suppliers.
 Use thermal oxidation by using a catalyst to consume the
Hydrocarbon Dewpoint Control free oxygen by reacting it with the hydrocarbon present
Heavy hydrocarbons (C6+) can be absorbed by solvents, to form CO2 and water.
which could lead to foaming in the sweetening unit. It is possi-  Use an iron-based oxidation catalyst that is activated
ble to reduce the heavy hydrocarbon content of the incoming with hydrogen sulfide or other organic sulfur compounds
gas through cooling (via Joule-Thomson expansion, propane re- to remove the free oxygen.
frigeration, or turbo-expansion as described in Section 16), and
subsequent condensation of the heavy components. The con-  Remove other reactants that cause problems with the
densed liquids are removed, and the gas is warmed above the presence of oxygen. By removing offending components
saturation temperature before going to the sweetening unit. such as water or H2 S that react with oxygen, the pres-
ence of small amounts of oxygen might be tolerated.
An alternative means to remove gaseous heavy hydrocar-
bons is through adsorption. Silica gel beds may be used in par-  Treat the symptom.
allel such that one bed is regenerated while the other is in ser-
 Corrosion inhibitors, filtration and/or alternate schemes
vice. The beds are regenerated by heating and desorbing the
may be utilized to stop or offset any adverse effects of
hydrocarbons. The heavy hydrocarbons are recovered from the
oxygen contamination.
regeneration gas via condensation.
A GPA report (RR-201) reviewing technology for oxygen
Another alternative is to use a composite membrane where
removal from natural gas is listed at the end of this section.
a rubbery polymer provides the selective membrane layer. This
technology is used in fuel gas conditioning commercially, and is
described in more detail in Section 16, Hydrocarbon Recovery. MERCURY REMOVAL
It is not unusual for gas streams to contain 1 to 10 micro-
Oxygen Contamination grams/Nm3 (approx. 0.1 to 1.0 ppbv) of mercury. Some gas
Oxygen entry into a hydrocarbon system is often trouble- streams have been reported to have over 100 micrograms/m3 (ap-
some. If liquid water is present, severe corrosion may occur. If prox. 10 ppbv). The mercury can attack aluminum in down-
H2S or sulfur is present, corrosion by a different mechanism or stream plate fin heat exchangers used in most modern cryogenic
sulfur deposition and plugging may occur. Oxygen contamina- hydrocarbon recovery plants as described in Section 16. In order
tion may be addressed by several different approaches, but the for the attack to occur, the mercury must be present as a free

21-3
liquid. This situation cannot occur above –40 °F. Technically, organic mercury is achieved. By first drying the gas the degree
mercury containing feedstocks can be handled without alumi- of mercury removal increases. The sulfur impregnate reacts
num corrosion. Mercury containing equipment, which is kept at with the mercury to produce a mercury sulfide that is fixed in
low temperature can be decontaminated by carrying out a cold, the carbon microstructure.
then warm purge with bone dry gas. However, this is not a prac-
tical method to be assured that mercury attack does not occur. Puraspec®
The mercury in the feed gas can be removed with a mercury Johnson Matthey’s (JM’s) PURASPEC® fixed-bed technolo-
removal bed. The bed uses a sulfur based trapping material gy is widely used within the industry to provide elemental mer-
which reacts with the mercury to form cinnabar (HgS) on the cury removal down to less than 10 ng/Nm 3. The absorbent is
bed. The trapping material is carried on activated carbon, zeo- based on a mixed metal sulfide which reacts with the mercury
lite or alumina. The trapping bed is usually located downstream to form cinnabar. Since the active component is present as a
of the dehydration. In this location, the gas is free of entrained sulfide, the material can be used on either wet or dry gas. If any
liquids and water. Locating the bed in other locations is very H2S is present in the feed gas, the mixed-metal oxide, which is
dependent on the material used as recommended by the vendor. easier to load, can be used in place of the pre-sulfided material.
A typical adsorbent vessel is depicted in Fig. 21-2, and may be JM also provides a full reprocessing service for the spent Hg
designed to remove the mercury down to 10 ng/Nm3 (10 nano- guard. PURASPEC has 500 references worldwide.
grams per normal cubic meters).
Desorex®
Each vendor has criteria for sizing beds for their material.
Typical sizing criteria used in the industry are to design for a Activated carbon provides only a limited storage capacity for
superficial flow velocity of about 50 ft/min and a residence time of the strictly physical adsorption of mercury. Desorex ® HGD2S
10 seconds. With the rather small mass of mercury which is typi- and HGD4S from Donau Carbon can be employed to bind mer-
cally removed, the beds can last many years between change cury through the process of chemical adsorption involving oxi-
outs. Note that spent materials must be properly handled, and dation and adsorption in the form of stable compound or fixa-
some vendors will provide reprocessing services. tion in metallic form as an amalgam. These Desorex ® products
have been used to purify natural gases to levels as low as 10 ng/
Calgon HGR® Nm3 of mercury.
Solid adsorbents can remove mercury from gas to produce HgSIV®
residuals in the range of 1 to 10 ng/Nm3. Calgon sulfur impreg-
nated HGR® (4 x 10 mesh) and HGR®-P (4 mm dia.) carbons are UOP supplies HgSIV® adsorbents which are molecular
used for mercury removal and indicate designs removing mer- sieves coated with elemental silver. Mercury in the gas is
cury down to very low levels. Removal of both inorganic and trapped by amalgamation with the silver. The adsorbent also
serves the dual function of dehydrating the gas. HgSIV ® is re-
generated thermally, just like molecular sieves for dehydration.
FIG. 21-2 This material can be added as a layer to existing molecular
Mercury Removal Bed sieve dryers.5 However, one must take care to appropriately
handle the regeneration gas in this case, as it will contain mer-
cury, which when desorbed will come off as a concentrated
spike.
Instrument Nozzle

UOP also offers GB-346S, a non-regenerable, pre-sulfided cop-


per material for removing mercury from liquid hydrocarbons.
Inlet Gas AxTrap 271 and 273
Another mercury trapping material, AxTrap 273 is offered
Upper Manway
by Axens, which is sulfur supported on a mesoporous alumina.
The advantage of this mesoporous alumina based product is its
resistance to capillary condensation.6 The larger pore size of
this material, compared to carbon-based trapping materials,
permits utilization at near dew point conditions. The trapping
component is anchored on the alumina carrier making it com-
pletely insoluble in liquid hydrocarbons and water. The mate-
rial has been subjected at gas plant sites to both DEA and liquid
hydrocarbon carry-over with no active phase leaching. This
Lower Manway
same material has been used to eliminate elemental mercury
from LPG and full range condensates.
AxTrap 271 also offered for use by Axens as a guard bed
material used for mercury removal from gas hydrocarbon
streams where the active trapping phase is a metal sulfide sup-
ported on alumina. This material provides a high efficiency for
the removal of mercury from all types of gaseous flows, includ-
ing natural gas.

Outlet Gas

21-4
Organic Mercury Removal permitting requirements and economic impact of hazardous
waste disposal on a project must not be overlooked.
Removal of all forms of organic mercury compounds from
natural gases and liquids requires firstly the conversion of the The importance of having an accurate analysis of the inlet
compounds to elemental metallic mercury followed by trapping gas stream cannot be overstressed. Process selection and eco-
materials to remove the metallic mercury formed. This requires nomics depend on knowing all components present in the gas.
in the first stage some hydrogen for organo-mercury hydroge- Impurities such as COS, CS2 and mercaptans (even in very
nolysis with a suitable catalyst. The first stage catalyst such as small concentrations) can have a significant impact on the pro-
MEP 841 also traps gas-phase arsenic and lead impurities in cess design of both the gas treating and downstream processing
the feed. The two-stage impurities-removal process is called facilities.7,8
RAM and is available from Axens. If the gas processing facility is to be used in conjunction with
liquids recovery, the requirements for H2S, CO2, and mercaptan
GAS TREATING — PROCESS OPTIONS removal may be affected. In liquid recovery plants, varying
amounts of H2S, CO2, and other sulfur compounds will end up
The gas treating process can affect the design of the entire
in the liquid product. Failure to remove these components prior
gas processing facility, including the methods chosen for acid
to liquids recovery may require liquid product treating in order
gas disposal and sulfur recovery, dehydration, liquids recovery,
to meet product specifications. In many instances, liquid treat-
liquids fractionation and liquid product treating. Some of the
ing may be required anyway.
factors to be considered in selecting the gas treating process
are: When sulfur recovery is required, the composition of the
acid gas stream feeding the sulfur plant must be considered.
 Air pollution regulations regarding sulfur compound
With CO2 concentrations greater than 80% in the acid gas, the
emissions and/or SRU/Tail Gas Clean Up (TGCU)
requirements possibility of selective treating should be considered to raise the
H2S concentration to the sulfur recovery unit (SRU). This may
 Type and concentration of impurities in the sour gas involve a multi-stage gas treating system in which the gas exit-
ing the first stage is enriched by passing it through another
 Specifications for the residue gas
absorption solvent loop. This is known as “acid gas enrichment,”
 Disposition of the acid gas or “AGE.”
 Temperature and pressure at which the sour gas is avail- High concentrations of hydrocarbons can cause design and
able and at which the sweet gas must be delivered operating problems for the SRU. The effect of these components
 Volume of gas to be processed must be weighed when selecting the gas treating process to be
used. Further discussion of this can be found in Section 22.
 Hydrocarbon composition of the gas
Selecting a gas treating process can be complicated by gas
 Selectivity required for acid gas removal composition and operating conditions. High partial pressures
 Capital cost and operating cost (50 psi) of acid gases enhance the possibility of using a physical
solvent; however, the presence of significant quantities of heavy
 Operability/maintainability/reliability hydrocarbons in the feed discourages using physical solvents.
 Royalty cost for using the process Low partial pressures of acid gases and low outlet specifications
generally require the use of amines for adequate treating. Pro-
 Liquid product specifications cess selection is not easy and a number of variables must be
weighed prior to making a process selection. Fig. 21-3 summa-
 Disposal of byproducts considered hazardous chemicals
rizes capabilities for a number of treating processes.
Any process which requires disposal of waste chemicals
must determine if the chemical is considered “hazardous.” The

FIG. 21-3
Process Capabilities for Gas Treating

Normally Capable of Removes Mercaptans Solution Degraded (By


Selective H2S Removal
Meeting 4 ppmv H2S and COS COS & CS2)
Primary Amine Yes Partial No Yes
Secondary Amine Yes Partial No Some
Tertiary Amine Yes Partial Yes* No
Hybrid/Mixed Yes Yes Yes* Some
Physical Solvent Yes Yes Yes* No
Solid Bed Yes Yes Yes* N/A
Liquid Redox Yes No Yes CO2 at high conc.
Sacrificial Yes Partial Yes N/A
* Some selectivity exhibited

21-5
Discussion of pH For each liter of solution the change in OH– (H+) required is
(10-2) – (10-7) = 1.0 • 10-2 gram moles/liter
Controlling pH is very important in the aqueous processes
discussed in this section. The following is offered to assist in The total requirement of HCl is
understanding electrolyte solutions and pH.
(1.9 • 104) liter • (1.0 • 10–2) (g mole/liter) = 190 g mole
An electrolyte is a substance or material that will provide
or
ionic conductivity when dissolved in water. Both bases and ac-
ids, if they ionize in water, can be electrolytes. In water, acids (190 g mole)(36.5 g/gmole)
= 15.3 pounds HCl
ionize or split, into H+ and the anion. The H+ combines with a 454 (gram/pound)
water molecule to form H3O+ which is usually written as H+ and
is referred to as a hydrogen ion, or proton. Water-soluble bases, Note that at a pH of 7, all of a weak acid (base) would prob-
on the other hand, ionize in water to produce hydroxyl or OH – ably not be neutralized. The pH required to have all of a weak
ions and a cation. Pure water ionizes such that the concentra- acid (base) neutralized will vary with the acid but will usually
tion of H+ (and OH–) in the solution is 10–7 gram ions/liter. be less (greater) than 7. In the example all of the HCl is neutral-
ized because it is completely ionized in the water solution.
The method used for measuring hydrogen and hydroxyl ion
concentrations uses pH (from the French pouvoir hydrogene),
where the pH of a solution is the logarithm (base 10) of the re-
CHEMICAL SOLVENT PROCESSES
ciprocal of the hydrogen ion concentration (gram mole/liter). Chemical solvent processes remove the H2S and/or CO2 from
For pure water, then, the pH would be: the gas stream by chemical reaction with a material in the sol-
vent solution. The reactions may be reversible or irreversible.
pH = log (1/ [H+]) = 7
In reversible reactions the reactive material removes CO2 and/
When a water molecule dissociates, one proton and one hy- or H2S in the contactor at high partial pressure and/or low tem-
droxyl ion are formed. The concentration of OH– in pure water, perature. The reaction is reversed by high temperature and/or
then, is also 10–7 mole/liter. low pressure in the stripper. In irreversible processes the chem-
ical reaction is not reversed and removal of the H2S and/or CO2
A strong acid (or strong base) is one which ionizes complete- requires continuous makeup of the reacting material. Fig. 21-5
ly in water solution. Typical are HCl or NaOH. At an acid con- shows the process flow for a typical reversible chemical solvent
centration of 0.1 mole/liter, the pH of a strong acid will be 1. The reaction process. Fig. 21-6 is a table of physical properties of
following table will be helpful in understanding the relative pure gas treating chemicals. Figs. 21-7 through 21-9 show va-
concentrations of H+ and OH– in solutions of different pH. por pressures at various temperatures and freezing points and
Concentration, mole/liter specific gravity for some of the treating chemicals.
pH
H+ OH– Aqueous Alkanolamine Processes
–1
1 1.0 • 10 1.0 • 10–13 Originally applied to gas treating in 1930 by Bottoms 9 al-
Acid Side (Excess 2 1.0 • 10–2 1.0 • 10–12 kanolamines have become the most widely used solvents for the
H+) 3 1.0 • 10–3 1.0 • 10–11
removal of acid gases from natural gas streams. 10 Triethanol-
amine (TEA) was the first used commercially for gas treating. It
4 1.0 • 10–4 1.0 • 10–10 has been displaced for conventional applications by other al-
5 1.0 • 10 –5
1.0 • 10–9 kanolamines such as monoethanolamine (MEA), diethanol-
amine (DEA), diisopropanolamine (DIPA), diglycolamine ®
6 1.0 • 10–6 1.0 • 10–8 (DGA®) and methyldiethanolamine (MDEA). Fig. 21-4 lists ap-
–7
Neutral Solution 7 1.0 • 10 1.0 • 10–7 proximate guidelines for a number of alkanolamine processes.
8 1.0 • 10–8 1.0 • 10–6 The alkanolamine (hereafter amine) solvent processes are
9 1.0 • 10 –9
1.0 • 10–5 particularly applicable where acid gas partial pressures are low
and/or low levels of acid gas are desired in the residue gas. Be-
10 1.0 • 10–10 1.0 • 10–4 cause the water content of the solution minimizes heavy hydro-
–11
11 1.0 • 10 1.0 • 10–3 carbon absorption, these processes are well suited for gases rich
–12 in heavier hydrocarbons. Some amines can be used to selective-
Basic Side 12 1.0 • 10 1.0 • 10–2
ly remove H2S in the presence of CO2.
(excess OH-) 13 1.0 • 10–13 1.0 • 10–1
Chemistry — The overall equilibrium reactions applicable
for H2S and CO2 and primary and secondary amines are shown
Example 21-1 — 5,000 gallons of amine solution with a pH of 12 below with a primary amine.11 A qualitative estimation of the
is to be neutralized by the addition of hydrochloric acid (HCl). velocity of the reaction is given.
How many pounds of pure HCl will be required? For hydrogen sulfide removal
Note: This is simply an example calculation; there is no RNH2 + H2S ↔ RNH 3+ + HS – Fast Eq 21-1
practical reason for doing this in a gas treating plant.
– ––
RNH2 + HS ↔ RNH + S 3
+
Fast Eq 21-2
MW of HCl = 36.5 g/gmole
The overall reactions between H2S and amines are simple
Solution steps since H2S reacts directly and rapidly with all amines to form the
bisulfide by Equation 21-1 and the sulfide by Equation 21-2.
5,000 gal. • 3.79 (liter/gal) = 1.9 • 104 liters

21-6
For carbon dioxide removal The other overall reactions leading to bicarbonate (Equation
– 21-4) and to carbonate (Equation 21-5) are slow because they
2 RNH2 + CO2 ↔ RNH + RNHCOO Fast 3
+
Eq 21-3 have to proceed through the hydration of CO2.

RNH2 + CO2 + H2O ↔ RNH
3
+
+ HCO
3 Slow Eq 21-4 If there was no further hydrolysis, Equation 21-3 suggests
– ––
RNH2 + HCO ↔ RNH + CO 3
+
3 3 Slow Eq 21-5 that there would be theoretical limit to the chemical loading ca-
pacity of the primary and secondary amine solutions to 0.5 mole
Concerning the chemical reactions with CO2, primary CO2 per mole of amine, even at relatively high partial pressures
amines (RNH2 ) such as MEA and DGA® agent, and secondary of CO2 in the gas to be treated.
amines (RR’NH) such as DEA and DIPA, differ from tertiary
amines (RR’R”N) such as TEA and MDEA. Tertiary Amines
Primary and Secondary Amines Unlike primary and secondary amines, the nitrogen ( N ) in
tertiary amines ( RR’R”N ) has no attached hydrogen ( H ) to
With the primary and secondary amines, the predominant rapidly form carbamate as per overall Equation 21-3. As a con-
overall reaction with CO2 (Equation 21-3) rapidly leads to the sequence, the removal of CO2 by tertiary amines can only follow
formation of a stable carbamate which is slow to further hydro-
lyze to bicarbonate.

FIG. 21-4
(Note 1)
Approximate Guidelines for Amine Processes

MEA DEA(9) DGA® Sulfinol® MDEA


(2)
Acid gas pickup, scf/gal @ 100 °F, normal range 3.1–4.3 6.7– 7.5 4.7–7.3 4–17 3–7.5
(3)
Acid gas pickup, mols/mol amine, normal range 0.33–0.40 0.20–0.80 0.25–0.38 NA 0.20–0.60
Lean solution residual acid gas, mol/mol amine,
0.12± 0.01± 0.06± NA 0.005–0.01
normal range(4)
Rich solution acid gas loading, mol/mol amine,
0.45–0.52 0.21–0.81 0.31–0.44 NA 0.21–0.61
normal range(3)
3 comps.,
Max. solution concentration, wt% 25 40 60 65
varies
Approximate reboiler heat duty, Btu/gal lean solution (5) 1,000–1,200 840–1,000 1,100–1,300 350–750 800–900
Steam heated reboiler tube bundle, approx. average heat flux,
9,000–10,000 6,300–7,400 9,000–10,000 9,000–10,000 6,300–7,400
Q/A = Btu/hr-ft2 (6)
Direct fired reboiler fire tube, average heat flux,
8,000–10,000 6,300–7,400 8,000–10,000 8,000–10,000 6,300–7,400
Q/A = Btu/hr-ft2 (6)
Reclaimer, steam bundle or fire tube, average heat flux,
6,000–9,000 NA(7) 6,000–8,000 NA NA(7)
Q/A = Btu/hr-ft2 (6)
Reboiler temperature, normal operating range, °F (8) 225–260 230–260 250–270 230–280 230–270
(10)
Heats of reaction; approximate:
610 555 674 NA 530
Btu/lb H2S
825 730 850 NA 610
Btu/lb CO2
NA — not applicable or not available

NOTES:
1. These data alone should not be used for specific design purposes. Many design factors must be considered for actual plant design.
2. Dependent upon acid gas partial pressures and solution concentrations.
3. Dependent upon acid gas partial pressures and corrosiveness of solution. Care must be taken with materials at high amine loadings as corrosivity may be
high. The size of the plant and H2S:CO2 ratio will also factor in to maximum design loading and materials of construction.
4. Varies with stripper overhead reflux ratio. Low residual acid gas contents require more stripper trays and/or higher reflux ratios yielding larger reboiler
duties.
5. Varies with stripper overhead reflux ratios, rich solution feed temperature to stripper and reboiler temperature.
6. Maximum point heat flux can reach 20,000–25,000 Btu/hr-ft2 at highest flame temperature at the inlet of a direct fired fire tube. The most satisfactory design
of firetube heating elements employs a zone by zone calculation based on thermal efficiency desired and limiting the maximum tube wall temperature as
required by the solution to prevent thermal degradation. The average heat flux, Q/A, is a result of these calculations.
7. Reclaimers are not used in DEA and MDEA systems.
8. Reboiler temperatures are dependent on solution conc. flare/vent line back pressure and/or residual CO 2 content required. It is good practice to operate the
reboiler at as low a temperature as possible.
9. According to Total.
10. B.L. Crynes and R.N. Maddox, Oil Gas J., p. 65–67, Dec. 15 (1969). The heats of reaction vary with acid gas loading and solution concentration. The values
shown are average10.

21-7
the slow route to bicarbonate by Equation 21-4 and carbonate ent solutions though some designs incorporate multiple feeds
by Equation 21-5. and contactor sections. Note that commercially-available process
simulators are available to model these solvent processes.
The slow rate of the reaction leading to bicarbonate is the
underlying reason why tertiary amines can be considered for Sour natural gas enters through an inlet separator for the
selective H2S removal. By adjusting absorption contact time, removal of liquids and/or solids. From the separator, the gas
this selectivity can be used to full advantage when near total stream is often heated about 10 °F to reduce the potential for hy-
CO2 removal is not necessary. drocarbon condensation as discussed earlier in this section. The
gas then enters the bottom of the contactor where it contacts the
However, the slow route to bicarbonate theoretically allows amine solution flowing down from the top of the column. The
an equilibrium chemical loading ratio of one mole of CO2 per acid gas components in the gas react with the amine to form a
mole of amine. Furthermore, at high CO2 partial pressure, the regenerable salt. As the gas continues to pass up the contactor,
physical solubility of CO2 in tertiary amines is far greater than more acid gases chemically react with the amine. The sweetened
in the primary and secondary amines, thus enhancing the CO2 gas leaves the top of the contactor and passes through an outlet
loading. Therefore, in the case of gases to be treated for bulk separator to catch any solution which may be carried over.
CO2 removal, large amounts of CO2 can be liberated from the
rich solvent using a simple flash, thereby reducing the thermal The sweet gas leaving the contactor is saturated with water
regeneration duty with consequent energy savings. so dehydration, discussed in Section 20, is normally required
prior to sale. If the amine losses are excessive, a water wash
Activated Tertiary Amines section as shown in Fig. 21-10 is typically added to the column
to attempt to recover some of the vaporized and/or entrained
The use of activators bypasses the slow reaction to bicarbon-
amine from the gas leaving the contactor. The water wash sec-
ate for tertiary amines. Activators are generally primary or sec-
tion generally consists of three or four trays at the top of the
ondary amines. They increase both the hydrolysis of the carba-
contactor. Trays can be sieve type, valves or other design as
mate, and the rate of hydration of dissolved CO 2. This makes
recommended by a vendor. Weirs are 2.5 to 3 inches high. It is
the activated tertiary amines especially suitable for efficient
recommended to install a demister pad on the vapor outlet.
and economic bulk removal when selectivity is not required (see
discussion on MDEA). Amine vapors and small droplets are dissolved and co-
alesced in water running in a closed loop with a circulation
Amine Process Flow Conftguration pump in the water wash system. To control amine concentra-
The general process flow for an amine treating plant is shown tion from building up in the water, some of the water is purged
in Fig. 21-5. The basic flow configuration varies little for differ- and made up. The purge is normally routed to the Flash Tank

FIG. 21-5
Example Gas Sweetening by Chemical Reaction

Surge Tank
Filtration

(as required)

21-8
FIG. 21-6
Physical Properties of Pure Gas Treating Chemicals
MEA DEA TEA DGA® DIPA Selexol®
Formula HOC2H4NH2 (HOC2H4)2NH (HOC2H4)3N H(OC2H4)2NH2 (HOC3H6)2NH Polyethylene
glycol derivative
Molecular Wt 61.08 105.14 148.19 105.14 133.19 280
Boiling point @ 760 mm Hg, °F 338.9 516.2 (decomposes) 680 (decomposes) 430 479.7 518
Freezing point, °F 50.9 82.4 72.3 9.5 107.6 –20
Critical constants
Pressure, psia 868 474.7 355 547.11 546.8 —
Temperature, °F 662 827.8 957.7 756.6 750.6 —
Density @ 20 °C, gm/cc. 1.018 1.095 1.124 1.058 @ 60 °F 0.999 @ 30 °C 1.031 @ 77 °F
Weight, lb/gal 8.48 @ 60 °F 9.09 @ 60 °F 9.37 @ 68 °F 8.82 @ 60 °F 8.60 @ 77 °F
Specific gravity 20 °C/20 °C 1.0179 1.0919 (30/20 °C) 1.1258 1.0572 0.989 @ 45 °C/20 °C —
Specific heat @ 60 °F, Btu/lb/°F 0.608 @ 68 °F 0.600 0.70 0.571 0.69 @ 30 °C 0.49 @ 41 °F
Thermal conductivity
Btu/[(hr • sq ft • °F)/ft] @ 68 °F 0.148 0.127 — 0.121 — 0.11 @ 77 °F
Latent heat of vaporization, 180 @ 760 288 @ 73 230 @ 73 219 @ 760 185 @ 760 mmHg —
Btu/lb mmHg mmHg mmHg mmHg
Heat of reaction, Btu/lb of Acid Gas
H2S 400 –674 — –190 @ 77 °F
CO2 630 –850 — –160 @ 77 °F
Viscosity, cp 24.1 @ 68 °F 350 @ 68 °F 1013 @ 68 °F 40 @ 60 °F 870 @ 86 °F 5.8 @ 77 °F
(at 90% wt. (at 95% wt. 198 @ 113 °F
solution) solution) 86 @ 129 °F
Refractive index, Nd 68 °F 1.4539 1.4776 1.4852 1.4598 1.4542 @ 113 °F —
Flash point, COC, °F 200 298 365 260 255 304

Propylene 10% Sodium


Carbonate MDEA Sulfolane® Methanol Hydroxide Flexsorb®SE
Formula C3H6CO3 (HOC2H4)2NCH3 C4H8SO2 CH3OH Proprietary
Molecular Wt 102.09 119.16 120.17 32.04 19.05 >130
Boiling point @ 760 mm 467 477 545 148.1 217 446
Hg, °F
Freezing point, °F –56.6 –9.3 81.7 –143.8 14 32
Critical constants —
Pressure, psia — 767.3 1153.9
Temperature, °F 1013.8 464
Density @ 20 °C, gm/cc. 1.2057
Weight, lb/gal 8.68 10.623 @ 30 °C/30 °C 9.254 7.81 @ 60 °F
Specific gravity 1.203 1.0418 1.268 0.7917 1.110
20 °C/20 °C
Specific heat @ 60 °F, 0.335 0.535 0.35 @ 30 °C 0.59 @ 5–10 °C 0.897
Btu/lb/°F
Thermal conductivity
Btu/[(hr • sq ft • °F)/ft] 0.12 @ 50 °F 0.159 0.114 @ 100 °F 0.124
@ 68 °F
Latent heat of 208 @ 760 mmHg 204 225.7 @ 212 °F 474 @ 760 mmHg 172 @
vaporization, Btu/lb 760 mmHg
Heat of reaction, Btu/lb
of Acid Gas —
H2S
CO2
Viscosity, cp 1.67 @ 100 °F 1.01 @ 68 °F 10.3 @ 86 °F 0.6 @ 68 °F 1.83 @ 68 °F 127 @ 60 °F
33.8 @ 104 °F 6.1 @ 122 °F 0.97 @ 122 °F 37 @ 100 °F
2.5 @ 212 °F 0.40 @ 212 °F
1.4 @ 302 °F
0.97 @ 392 °F
Refractive index, Nd 68 °F 1.4209 1.469 1.481 @ 86 °F 1.3286
Flash point, COC, °F 270 265 350 58 210

21-9
FIG. 21-7
Vapor Pressures of Gas Treating Chemicals

Temperature, °F

Temperature, °F

21-10
FIG. 21-8 (Drum). This post-sweetening water wash system can be de-
Freezing Points of Aqueous Amine Solutions signed using the same information as provided on pages 21-2
and 21-3.
Note that the lean amine coming into the top of the contac-
tor must be at a sufficiently low loading and temperature such
that the vapor pressure of the acid gas above the amine is low
enough to meet the treated gas specification (e.g., 4 ppm H2S,
and in the case of LNG, 50–100 ppm CO2). If the loading/tem-
perature criteria are not met, no amount of solvent will reduce
acid gas concentration adequately to meet the required specifi-
cation. This is known as a “lean end pinch,” since there is not
sufficient mass-transfer driving force to remove the residual
acid gases to the desired level.
As the solvent moves down the column and reacts with the
H2S and CO2, the exothermic reactions increase the solvent
temperature. Since raw gas coming into the bottom of the con-
tactor cools the solvent, there is usually a temperature “bulge”
above the gas inlet. Increased temperatures tend to increase
the vapor pressure of acid gases above the enriched solvent, so
it is possible that the driving force for mass transfer is reduced
to near zero, resulting in a “rich end pinch.” In this case, addi-
tional solvent will improve the situation by reducing the rich
loading and temperature in that portion of the column.
The maximum attainable pure component loading is limited
by the equilibrium solubility of H2S and CO2 at the absorber
bottoms conditions, which may be reached in some high-load
applications. Fig. 21-11 is from GPA research report RR-104 on
MEA, DGA® & MDEA along with the DEA data from the 12th
Edition of the GPSA Data Book for the equilibrium solubility of
H2S and CO2. Fig. 21-11 shows CO2 partial pressure above 15
wt% MEA as a function of CO2 loading for three different tem-
peratures. It illustrates the typical behavior of acid gases in
FIG. 21-9
aqueous amine solutions. This type of graph can be used to de-
Specific Gravity of Aqueous Amine Solutions termine the equilibrium value of acid gas concentration in the
treated gas (lean side), as well as the maximum rich load at-
tainable (rich side) for a given feed gas condition.
Data from Fig. 21-12 is also extracted from GPA RR-104 and
shows partial pressures of H2S or CO2 above different amines at
different conditions. However, it should be noted that both spe-
cies are usually present, and the equilibrium limit for each spe-
cies is impacted by the presence of the other.

FIG. 21-10
Typical Water Wash for Sweet Gas Leaving Amine
Contactor

Treated Gas

Water Make-up

Lean
Amine

Purge to Flash Drum

21-11
FIG. 21-11 added to the MEA reclaimer to provide a pH of approximately
Solubility of CO2 in 2.5 N MEA 8–9; no such addition is required for the DGA ® reclaimer sys-
tem. Reclaimers generally operate on a side stream of 1–3% of
Solution at 25, 60, and 80 °C the total amine circulation rate.13 Reclaimer sizing depends on
the total inventory of the plant and the rate of degradation
expected.
FIG. 21-12
Equilibrium Pure Component Loading

40 wt% DEA @ 190 °F


H2S partial pressure (psia) 45 145 220
mol H2S /mol amine 0.66 0.8 0.97
CO2 partial pressure (psia) 45 90 145
mol CO2/mol amine 0.49 0.55 0.6

15 wt% MEA @ 176 °F


H2S partial pressure (psia) 0.96 6.87 67.4
mol H2S /mol amine 0.717 0.995 1.187
CO2 partial pressure (psia) 36 170 254
mol CO2/mol amine 0.636 0.787 0.832

60 wt% DGA® @ 122 °F


H2S partial pressure (psia) 2.8 12.9 58.8
mol H2S /mol amine 0.435 0.756 0.986
CO2 partial pressure (psia) 26.6 115 484
mol CO2/mol amine 0.5984 0.668 0.773
Regardless, it is important to note most conventional
amine plants operate at significantly lower loadings than
20 wt% MDEA @ 150 °F
the equilibrium limit.
H2S partial pressure (psia) 3.24 26.3 138.1
Rich amine solution leaving the contactor flows through a mol H2S /mol amine 0.435 0.756 1.178
flash drum to flash off light hydrocarbons like methane and to CO2 partial pressure (psia) 6.92 24.26 148.4
allow heavier hydrocarbons to be skimmed off as a separate liq- mol CO2/mol amine 0.4433 0.706 0.999
uid phase. From the flash drum, the rich solution passes
through the rich/lean exchanger where heat is transferred from
the hot lean solution. The heated rich amine goes to the upper Reclaimer operation is a semi-continuous batch operation.
portion of the stripper. As the solution flows down the column The reclaimer is filled with hot amine solution and, if neces-
to the reboiler, it is stripped of H2S and CO2. The amine solution sary, soda ash is added. As the temperature in the reclaimer
leaves the bottom of the stripper as lean solution. This lean so- increases, the liquid will begin to distill. Overhead vapors can
lution is then passed through the rich/lean exchanger and a be condensed and pumped back into the amine system, but gen-
lean cooler to reduce the lean solution temperature to approxi- erally the reclaimer is operated at slightly above stripper col-
mately 10 °F warmer than the inlet gas temperature, to stay umn pressure and the vapors are returned to the stripper. The
above the hydrocarbon dew point. At this point, the lean solu- initial vapor composition is essentially water. Continued distil-
tion is returned to the contactor to repeat the cycle. lation will cause the solution to become more and more concen-
trated with amine. This raises the boiling point of the solution
Acid gas stripped from the amine passes out of the top of the and amine will begin to distill overhead. Fresh feed is continu-
stripper. It goes through a condenser and separator to cool the ally added until the boiling point of the material in the reclaim-
stream and recover water. The recovered water is usually re- er reboiler reaches 280 to 300 °F. At this point, distillation is
turned to the stripper as reflux. The acid gas from the reflux continued for a short time adding only water to help recover
separator is either vented, incinerated, sent to sulfur recovery residual amine in the reclaimer reboiler. The reclaimer is then
facilities, or compressed for sale or reinjected into a suitable cleaned, recharged, and the cycle is repeated.14
reservoir for enhanced (see acid gas injection) oil recovery proj-
ects or for sequestration. Reclaimer “sludge” removed during cleaning must be han-
dled with care. Disposal of the “sludge” must be in accordance
Reclaimer — A reclaimer is usually required for MEA and with the governing regulations.
DGA® amine-based systems. The reclaimer helps remove deg-
radation products from the solution and also aids in the remov- If needed a reclaiming company may be contracted to re-
al of heat stable salts, suspended solids, acids and iron com- move degradation products or heat-stable salts from the amine.
pounds. The distillative reclaimers in MEA and DGA® systems One type of reclaimer performs vacuum distillation on batches
differ. For MEA, a basic solution helps reverse the reactions of spent amine mixed with sufficient caustic to neutralize the
and deprotonate the amine. Soda ash and/or caustic soda is

21-12
excess acidity. Another type of reclaimer uses ion exchange The process flow for the DGA® treating process is similar to
resin beds to remove heat stable salts. that of the MEA treating process. The three major differences
are:
Amines Used
 Higher acid gas pick-up per gallon of amine can be ob-
Monoethanolamine — Gas sweetening with monoetha- tained by using 50–60% solution strength rather than
nolamine (MEA) is used where there are low contactor pres- 15–20% for MEA (more moles of amine per volume of
sures and/or stringent acid gas specifications. MEA removes solution).
both H2S and CO2 from gas streams. H2S concentrations well
below 4.0 ppmv can be achieved. CO2 concentrations as low as  The required treating circulation rate is lower. This is a
100 ppmv can be obtained at low to moderate pressures. COS direct function of higher amine concentration.
and CS2 are removed by MEA, but the reactions are irreversible  Reduced reboiler steam consumption.
so a reclaimer is used on a slip stream of the amine. Even with
a reclaimer, complete reversal of the reactions may not be Typical concentrations of DGA ® range from 50% to 60%
achieved. The result is solution loss and build-up of degradation DGA® by weight while in some cases as high as 70 wt% has
products in the system. Total acid gas pick up is traditionally been used. DGA® has an advantage for plants operating in cold
limited to 0.3–0.35 moles of acid gas/mole of MEA and solution climates where freezing of the solution could occur. The freez-
concentration is usually limited to 10–20 wt%. Corrosion inhibi- ing point for 50% DGA ® solution is –30 °F. Because of the high
tors can be used to allow much higher solution strengths and amine degradation rate DGA ® systems require reclaiming to
acid gas loadings. Because MEA has the highest vapor pressure remove the degradation product. DGA ® reacts with both CO2
of the amines used for gas treating, solution losses through va- and COS to form N, N’, bis (hydroxyethoxyethyl) urea, gener-
porization from the contactor and stripper can be high. This ally referred to as BHEEU.16 DGA® is recovered by reversing
problem can be reduced by using a water wash. the BHEEU reaction in the reclaimer.
Diethanolamine — This process employs an aqueous solu- Diisopropanolamine — Diisopropanolamine (DIPA) is a sec-
tion of diethanolamine (DEA). DEA will not treat to pipeline ondary amine which exhibits, though not as great as tertiary
quality gas specifications at as low a pressure as will MEA. amines, selectivity for H2S. This selectivity is attributed to the steric
hindrance of the chemical. See discussion on next page. DIPA is
Among the processes using DEA is the SNPA-DEA process often used as a component in hybrid solvents (See Hybrid Sol-
developed by Societe Nationale des Petroles d’Aquitaine (today vents on page 21-22).
Total) to treat the very sour gas which was discovered in Lacq
France in the 1950s. The original patents covered very high Methyldiethanolamine —Methyldiethanolamine (MDEA)
acid gas loading of 0.9 to 1.3 moles per mole of amine. This pro- is a tertiary amine which can be used to selectively remove H2S
cess is used for high pressure, high acid gas content streams to pipeline specifications at moderate to high pressure. If in-
having a relatively high ratio of H2S /CO2. The original process creased concentration of CO2 in the residue gas does cause a
has been progressively improved and Total (through Prosernat) problem with contract specifications or downstream processing,
uses higher DEA solution concentrations up to 40 wt% and a further treatment will be required. The H2S/CO2 ratio in the
high acid gas loading with corrosion control by appropriate de- acid gas can be 10–15 times as great as the H2S/CO2 ratio in the
sign and operating procedures. sour gas. Some of the benefits of selective removal of H2S
include:
The process flow scheme for conventional DEA plants re-
sembles that of the MEA process. The advantages and disad-  Reduced solution flow rates resulting from a reduction in
vantages of DEA as compared to MEA are: the amount of acid gas removed
 The mole/mole loadings typically used with DEA (0.35–  Smaller amine regeneration unit
0.80 mole/mole) are much higher than those normally
 Higher H2S concentrations in the acid gas resulting in
used (0.3–0.4) for MEA.
reduced problems in sulfur recovery
 Because DEA does not form a significant amount of non-
CO2 hydrolyzes much slower than H2S. This makes possible
regenerable degradation products, a reclaimer is not usu-
significant selectivity of tertiary amines for H2S. This fact is
ally required. If DEA has to be reclaimed it must be done
used by several companies who provide process designs using
under vacuum conditions.
MDEA for selective removal of H2S from gases containing both
 DEA is a secondary amine and a weaker base than MEA, H2S and CO2.
so less heat is required to strip the amine solution.
A feature of MDEA is that it can be partially regenerated in
 DEA forms a regenerable compound with COS and CS2 a simple flash. As a consequence the removal of bulk H 2S and
and can be used for the partial removal of COS and CS 2 CO2 may be achieved with modest heat input for regeneration.
without significant solution losses. However as MDEA solutions react only slowly with CO2 (see
chemistry) activators must be added to the MDEA solution to
Diglycolamine® — This process uses Diglycolamine® enhance CO2 absorption. If this is done, then the solvent is re-
brand [2-(2-aminoethoxy)] ethanol in an aqueous solution. ferred to as promoted or activated MDEA.
DGA® is a primary amine capable of removing not only H2S and
CO2, but also COS and mercaptans from gas and liquid streams. Triethanolamine — Triethanolamine (TEA) is a tertiary
Because of this, DGA® has been used in both natural and refin- amine and has exhibited selectivity for H2S over CO2 at low
ery gas applications. DGA® has been used to treat natural gas pressures. TEA was the first amine commercially used for gas
to 4.0 ppmv at pressures as low as 125 psig.15 DGA® has a great- sweetening. It was replaced by MEA and DEA because of its
er affinity for the absorption of aromatics, olefins, and heavy inability to remove H2S and CO2 to low outlet specifications.
hydrocarbons than the MEA and DEA systems. Therefore, ad- TEA has potential for the bulk removal of CO2 from gas streams.
equate carbon filtration should be included in the design of a It has been used in many ammonia plants for CO2 removal.
DGA® treating unit.

21-13
Formulated solvents and mixed amines — Formulated such as MDEA. These sterically hindered amines are very se-
Solvents is the name given to a new family of amine-based sol- lective for the removal of H 2S in the presence of CO 2. For low
vents. Their popularity is primarily due to equipment size re- pressure applications such as AGE and TGCU, the CO 2 slip can
duction, reduced corrosion and energy savings over most of the be as high as 95%. An example of this technology is
other amines. FLEXSORB®SE/SE Plus solvents, marketed by ExxonMobil
Research and Engineering Company. 18,19
All the advantages of MDEA are valid for the Formulated
Solvents, usually to a greater degree. Some formulations are
FIG. 21-13
capable at high pressure of slipping larger portions of inlet CO2
than generic MDEA to the outlet gas and at the same time re- Common Formulated Amines Applications
moving H2S to less than 4 ppmv. Under conditions of low ab-
Treating
sorber pressure and high CO2 /H2S ratios, such as Claus tail gas Gas Treating Specification/Application
Strategy
clean-up units, certain solvent formulations can slip up to 90%
of the incoming CO2 to the incinerator. Outlet H2S (4 PPM) & CO2 ( down to <50
Deep H2S and CO2
ppmv)/Treating high pressure sour gas w/
At the other extreme, certain formulations remove CO2 to a removal
H2S for downstream cryogenic processing
level not possible with MDEA, so that the sweet gas is suitable
for cryogenic plant feed. Formulations are also available for Outlet H2S (4 ppmv) & CO2 (0.5 to 2 mol%)/
Deep CO2 removal
CO2 removal in ammonia plants. Finally, there are solvent for- Treating high pressure sour gas w/H 2S to
w/some CO2 slip
mulations, which remove H2S to 4 ppmv pipeline specifications, pipeline specifications
while reducing high inlet CO2 concentrations to 2% for delivery Outlet CO2 down to <50 ppmv/Treating high
to a pipeline. Typical treating applications for the gas process- Deep CO2 Removal pressure gas w/CO2 upstream of cryogenic
ing industry, and the common treatment strategies employed processing
using formulated amines, are summarized in Fig. 21-13. Sev-
eral general approaches are commonly used in the solvent Outlet CO2 (2 mol%)/Treating high
CO2 removal with
formulations. pressure gas w/CO2 to pipeline
slip
specifications
To achieve very low CO2 concentrations in the treated gas,
the formulation may contain activators, such as piperazine or Outlet CO2 (100-1000 ppmv)/Treating high
Deep CO2 removal
primary/secondary amines to promote CO2 removal. pressure gas to produce pipeline quality gas
with bypass
(2 mol% CO2) using feed gas bypass
In order to enhance H2S removal, and thereby allow greater
CO2 slip, stripping agents, such as inorganic acids may be used. Outlet H2S (10 ppmv to 250 ppmv) w/high
Deep H2S removal
CO2 slip/Sulfur plant tail gas treating or
This need for a wide performance spectrum has led Formu- with high CO2 slip
AGE applications
lated Solvent suppliers to develop a large stable of different
MDEA-based solvent formulations or MDEA-based solvents. In
summary, benefits claimed by suppliers are: Acid Gas Enrichment
For New Plants Normally, Acid Gas Removal units (AGRs) remove essen-
tially all of the H2S and CO2 from the produced natural gas. As
 reduced corrosion discussed previously, AGRs can utilize a variety of solvents, in-
 reduced circulation rate cluding generic and formulated MDEA. In some cases, con-
trolled CO2 removal can be used using a selective solvent such
 lower energy requirements as FLEXSORB®SE or an MDEA based solvent to leave some of
 smaller equipment due to reduced circulation rates the CO2 in the sales gas. However, for gas fields with high CO2
to H2S ratios, the acid gas stream from the AGR regenerator
will have an unfavorably high CO2 to H2S ratio resulting in a
For Existing Plants poor quality feed to a Claus plant.
 increase in capacity, i.e., gas through-put or higher inlet In the last few decades, Acid Gas Enrichment (AGE) has
acid gas composition been used much more frequently to increase the H2S content in
high CO2 containing acid gas streams. As the name implies, acid
 reduced corrosion
gas enrichment concentrates the H2S from the AGR system by
 lower energy requirements and reduced circulation further gas treatment in a second amine unit utilizing a selective
rates amine solvent. Except for the use of the selective amine solvent,
an AGE unit is similar to other traditional amine treating units.
Formulated solvents are proprietary to the specific supplier Fig. 21-14 shows a simplified flow diagram of an acid gas enrich-
offering the product. Companies offering these products and/or ment unit. The AGR acid gas is fed to the base of an absorber
processes include INEOS, Huntsman Corporation, Dow Chemi- column equipped with either trays or packing where the H2S is
cal Company, UOP, BASF, Shell Global Solutions and Total via absorbed via counter-current contacting with the descending
Prosernat. amine solvent. The AGE absorber typically operates at low pres-
Sterically hindered amines — Other amines have been sure (~0.5 barg, 7 psig), compatible with the operating pressure
used to treat sour gas.17 One specialty amine uses steric hin- of the upstream AGR regenerator overhead system, but gener-
drance (see nomenclature) to slow the rate of CO2 absorption. ally somewhat higher to provide the required inlet pressure to
This type of amine and the associated technology is different the SRU, so that the main AGR doesn’t need to provide the extra
than Formulated Solvents, which create the desired formula- pressure drop. The selective amine in the AGE preferentially ab-
tions by blending different components with a standard amine

21-14
TREATED GAS ENRICHED
OVERHEAD
CONDENSER ACID GAS

MAKE-UP
AGE ABSORBER
WATER

LEAN CARBON FINES REFLUX DRUM


SOLUTION
TREATER FILTER LEAN SURGE
FILTER REGENERATOR
VESSEL

10 PURGE
WATER

Standalone AGE Flow Diagram


8 REFLUX
WASH
6
PUMP
PUMP

LEAN
COOLER

FIG. 21-14
21-15

LEAN
1
AMINE
1
AGR PUMP
ACID GAS
REBOILER

STEAM

CONDENSATE

RICH/LEAN
RICH EXCHANGER
AMINE
PUMP

SUMP FILTER

SUMP
PUMP

SUMP DRUM
sorbs the H2S and allows the CO2 to remain in the treated gas For activated MDEA (assuming 9:1 ratio of MDEA to DEA)
(also known as “CO2 slip”). The rich amine from the bottom of the
absorber is then pumped through a rich-lean heat exchanger and GPM = 51.7 • (Qy/x) Eq 21-9a
on to a regenerator tower. The regenerator produces an enriched
acid gas product overhead and the lean amine bottoms product (0.50 mol acid gas pick-up per mole mixture assumed)
to be recycled to the absorber.
Where:
To achieve the twin goals of low H2S in the treated gas and
low CO2 in the enriched acid gas, the AGE amine solvent must Q = Sour gas to be processed, MMscfd
maximize the selectivity for absorbing H2S. Unfortunately, the y = Acid gas concentration in sour gas, mole%
CO2 and H2S partial pressure driving forces in the AGE ab-
sorber work against achieving these goals simultaneously.20 As x = Amine concentration in liquid solution, wt% (Use Fig.
the gas moves up the absorber tower, the H2S partial pressure 21-4 to ensure amine concentration does not exceed max-
is decreasing reducing the mass transfer driving force. At the imum recommended concentration)
same time, the CO2 partial pressure is increasing, making CO2
pick-up more difficult to avoid, so the concentration factor After the amine circulation has been estimated, heat and
achieved in each acid gas enrichment step is limited. heat exchange requirements can be estimated from the informa-
tion in Fig. 21-15. Pump power requirements can be estimated
from Fig. 21-16.
SIMPLIFIED AGR DESIGN
CALCULATIONS Equations 21-6 to 21-9 normally provide conservative
(high) estimates of required circulation rate. They should not
A simplified procedure for making rough estimates of the be used if the combined H2S plus CO2 concentration in the
principal parameters for conventional MEA, DEA, DGA®, and gas is above 5 mole%. They also are limited to a maximum
MDEA amine treating facilities when both H2S and CO2 are amine concentration of about 30% by weight.
present in the gas is given below. It is based on excerpts from
Jones and Pearce,21 modified and extended by the Section 21 The diameter of an amine plant contactor, can be estimat-
Subcommittee22 in 2002. The procedure involves estimating the ed using the following equation:
amine circulation rate and using it as the principal variable in Contactor diameter
estimating other parameters. For estimating amine circulation D = 44 • √Q / √ Eq 21-10
rate, the following equations are suggested: c P

For MEA: Where:


GPM = 41 • (Qy/x) Eq 21-6 Q = MMscfd gas to contactor

0.33 mol acid gas pick-up per mole MEA assumed) P = Contactor pressure in psia
Dc = Contactor diameter in inches before rounding up to
For DEA (conventional): nearest 6 inches
GPM = 45 • (Qy/x) Eq 21-7 Similarly, the diameter of the regenerator below the feed
point can be estimated using the following equation:
(0.5 mol acid gas pick-up per mole DEA assumed)
Dr = 3.0 • √GPM Eq 21-11
For DEA (high loading):
Where:
GPM = 32 • (Qy/x) Eq 21-8
GPM = Amine circulation rate in gallons per minute
(0.7 mol acid gas pick-up per mole DEA assumed)
Dr = Regenerator bottom diameter in inches
The diameter of the section of the still above the feed point
For DGA®
can be estimated at 0.67 times the bottom diameter.
GPM = 55.8 • (Qy/x) Eq 21-9 Example 21-2 — 30.0 MMscfd of gas available at 850 psig and
(0.39 mol acid gas pick-up per mole DGA assumed) containing 0.6% H2S and 2.8% CO2 is to be sweetened using
20%, by weight, DEA solution. If a conventional DEA system is
to be used, what amine circulation rate is required, and what
will be the principal parameters for the DEA treating system?

FIG. 21-15
Estimated Heat Exchange Requirements for DEA FIG. 21-16
Estimated Power Requirements for DEA
Duty, Btu/hr Area, Sq ft.
Reboiler (Direct fired) 72,000 • GPM 11.30 • GPM Main Amine Solution Pumps GPM • PSI • 0.00065 = HP
Rich-Lean Amine HEX 45,000 • GPM 11.25 • GPM Amine Booster Pumps GPM • 0.06 = HP
Amine cooler (air cooled) 15,000 • GPM 10.20 • GPM Reflux Pumps GPM • 0.06 = HP
Reflux condenser 30,000 • GPM 5.20 • GPM Aerial Cooler GPM • 0.36 = HP

21-16
Solution: Jones et. al.23 have presented data to confirm the interactive
effect of H2S and CO2 in MEA solutions. Lee et. al.12,24 have pre-
Using Equation 21-7, the required solution circulation is: sented similar data for DEA solutions. Dingman et. al. 25 have
presented data for H2S and CO2 in equilibrium with commer-
GPM = 45(Qy/x) = 45(30 • 3.4/20) = 230 gallons of 20% cially used concentrations of DGA®. These data provide the ba-
sis for predicting the equilibrium concentrations of MEA, DEA,
DEA solution per minute and DGA® solutions when in contact with sour gases containing
Heat exchange requirements (from Fig. 21-15) both H2S and CO2.

Reboiler Jou, Otto, and Mather investigated the solubility of H2S and
CO2 in MDEA and published data in 1981.26 Later they investi-
H = 72,000 • 230 = 16.6 • 106 Btu/hr gated the solubility of mixtures of H2S and CO2 in MDEA, and
published data in 1986.27 The first paper presents solubilities
A = 11.3 • 230 = 2600 ft2
H2S in MDEA and solubility of CO2 in MDEA, whereas the sec-
Rich-Lean amine exchanger ond paper presents the results of varying mixtures of H2S and
CO2 and their solubility in MDEA.
H = 45,000 • 230 = 10.4 • 106Btu/hr
Kent and Eisenberg28 proposed a reaction equilibrium mod-
A = 11.25 • 230 = 2590 ft2 el to correlate/predict the vapor-liquid equilibrium between H2S
Amine cooler and CO2 and primary or secondary ethanolamines.

H = 15,000 • 230 = 3.45 • 106Btu/hr They tested the model extensively against data for MEA and
DEA with good results. This model allows for interpolation/ex-
A = 10.2 • 230 = 2350 ft2 trapolation of equilibrium data to compositions and tempera-
tures where no measurements have been made.
Reflux condenser
GPA reports on amine enthalpies of solution and acid gas
H = 30,000 • 230 = 6.9 • 106Btu/hr equilibrium solubility are listed at the end of this section.
A = 5.2 • 230 = 1200 ft2
Power requirements (Fig. 21-16) SOLUBILITY LIMITS OF
HYDROCARBONS AND MERCAPTANS
Main amine pumps
IN AMINE SOLUTIONS
HP = 230 • 850 • 0.00065 = 127
In general, all gas treating solvents will dissolve hydrocar-
Amine booster pumps bons and mercaptans in different amounts. Understanding the
solubility of these species in these gas treating solvents is im-
HP = 230 • 0.06 = 14 portant for many reasons including, but not limited to, being
Reflux pumps able to estimate treated gas product shrinkage (hydrocarbon
loss), estimating emissions of Hazardous Air Pollutants (HAPs
HP = 230 • 0.06 = 14 such as BTEX, n-Hexane, 224-Trimethylpentane, among oth-
Aerial cooler ers) for health, safety and permitting reasons, and estimating
the level BTEX or other hydrocarbons in the acid gas stream
HP = 230 • 0.36 = 83 that might have negative impacts to downstream processes
such as sulfur recovery. Extensive experimental data has re-
Contactor diameter cently been gathered to quantify hydrocarbon solubility in vari-
Dc = 44 • √30 /√865 = 44.4 inches or 48 inches rounded up ous gas treating amines, and the solubility of some hydrocar-
bons in amine solutions is documented in a number of GPA
Regenerator diameter below feed point: Research Reports (RR), including RR-180, RR-185, and Techni-
cal Paper TP-29. Similar data is available for mercaptans in
Dr = 3.0 • √230 = 45.5 inches or 48 inches (bottom) round- loaded and unloaded amines.
ed up to nearest 6 inches
The term “solubility” refers to the concentration, under
Regenerator diameter above feed point: specified conditions of equilibrium, of a solute dissolved in a
solvent, generally determined from VLE measurements, and
Dra = 0.67 • 45.5 = 30.5 inches or 36 inches (top) round- expressed in terms of equilibrium ratio (K) values or Henry’s
ed up to nearest 6 inches Law constant (H) values. With respect to the solubility of gases
or vapors in liquids, the solubility is a function of a number of
EQUILIBRIUM DATA FOR AMINE-SOUR variables including pressure, temperature, and the concentra-
GAS SYSTEMS tion of the solute in the gas phase. Because it is easier to get
more consistent and reliable VLLE data without disturbing
One of the peculiarities of amine treating systems is the in- equilibrium in the test cell for the low concentrations associated
teractive effects of one acid gas constituent with amine upon with hydrocarbon solubility in amines, most of the data result-
the equilibrium partial pressure of the other constituent. The ing from the referenced GPA Research Reports is “solubility
most commonly encountered sour gas constituents are H2S and limit” data. “Solubility limit” refers to the concentration of the
CO2. The capacity of a given amine for either one of the acid gas solute in the solvent where any additional increases in its gas-
constituents alone is much greater than when the two occur phase partial pressure will result in the formation of a second
together. liquid phase rather than further significant increases in the sol-

21-17
ute concentration in the solvent for a given temperature; little the “salting-in” effect, with one example of a typical effect
data below the solubility limit was gathered in the referenced on solubility limits shown in Fig. 21-18)
GPA Research Reports, and only for gaining a general under-
standing of the relationship between solubility and solubility  Hydrocarbon solubility in amine solutions is strongly de-
limit, such that “solubility” could be estimated based on the pendent on the specific amine used (Fig. 21-18)
“solubility limit” data.  Higher amine strength increases hydrocarbon solubility
While the solubility limit data forms a good basis for the (Fig. 21-18)
estimation of subsaturated solubility, the calculation of the  Higher temperature generally increases hydrocarbon
solubility at subsaturated conditions is not straightforward and solubility (Fig. 21-18)
is best done using a rigorous equation of state method. Howev-
er, the solubility limit data did lend itself to simple correlation;  Increased CO2 loading of MDEA decreases the solubility
this correlation for a few common hydrocarbon-amine solution of aromatic hydrocarbons, with higher temperature
systems is found in GPA Research Report RR-206. Using the showing a more marked change (Fig. 21-19)
solubility limit data, a simple method has been developed to
estimate subsaturated solubility and is described in detail in  Higher partial pressure of the hydrocarbon increases the
RR-206. However, due to the non-ideality of the vapor phase in solubility up to the point at which a separate liquid hy-
this system requiring determination of fugacity coefficients drocarbon phase forms (referred to here as the solubility
(Henry’s Law constants, when commonly defined as Hi = Pi/xi,1 limit, see Fig. 21-17)
are a function of temperature AND pressure for these systems)  While there is little influence on solubility limit due spe-
and the limited amount of VLE data, the simple method de- cifically to total system pressure (though it is measur-
scribed in RR-206 does not provide an accurate estimation of able), solubility can be strongly dependent on total sys-
subsaturated solubility across a wide range of pressures. In- tem pressure (Fig 21-17)
stead, the data in the referenced GPA Research Reports, and
solubility limit correlation in RR-206, can be used to check the  The aromatic hydrocarbons considered in the referenced
results of commercial simulation software, or as input data for Research Reports tended to be more soluble in amine so-
commercial simulation software for the creation of binary inter- lutions compared to non-aromatic compounds of the same
action parameters. Prediction of subsaturation solubility using carbon number, cyclic hydrocarbons tended to be more
the method outlined in RR-206 should only be considered when soluble than linear hydrocarbons, and olefins more solu-
other means of prediction are not available and when only ap- ble than paraffins (RR-180, RR-185, and TP-29)
proximate results are needed.  While solubility limits can readily be predicted by a sim-
A more complete summary and analysis of key data from ple model for some hydrocarbons and amines, estimates
these reports is contained in RR-206. of subsaturated solubility is better left to an equation of
state model that considers the relatively large impact of
Overall Hydrocarbon Solubility Trends the fugacity coefficient
Based on the data in the referenced GPA Research Reports, Additional details of consideration on this topic are given in
the following typical trends can be observed regarding the solu- TP-29. This reference also provides a more complete overall
bility of hydrocarbons in amine solutions: summary of the typical trends in hydrocarbon solubility in
amines and a review of the data in the literature. Further data
 Hydrocarbon solubility in amines follows similar trends and literature references can also be found in RR-195.
as hydrocarbon solubility in water, but the presence of
amine increases solubility significantly (also known as Overall Mercaptan and Other Sulfur
Species Solubility Trends
FIG. 21-17 Based on data in GPA Research Reports RR-164 and 207,
Equilibrium Ratio Values (K) for some the following trends were observed regarding the solubility of
Hydrocarbons in Amine Solutions mercaptans in amine solutions:
Tempera-  Mercaptans are only weakly acidic, so their solubility in
Hydrocar- Amine Pressure amines generally followed similar trends as hydrocarbons.
ture K
bon Solution (psia)
(F)
 Increased acid gas loadings slightly decreased the solu-
Toluene 65 w% DEA 77 75 20.2 bility of the mercaptans.
Toluene 65 w% DEA 140 75 64.3  The presence of mercaptans did not affect the value of the
Toluene 65 w% DEA 176 75 96.6 acid gas loading in the solution.

Toluene 50 w% MDEA 140 73 15.6  Similar trends were observed for dimethyl sulfide (DMS).
Toluene 50 w% MDEA 140 1019 3.9 In the absence of specific data, a general rule-of-thumb has
been that amine can be expected to pick up 20-30% of mercap-
Ethyl
50 w% MDEA 140 73 13.2 tans in the raw gas stream. If the treated gas exceeds the total
Benzene
sulfur specification, additional treating will be required.
Cyclohexane 50 w% MDEA 140 73 316.6
Benzene* 50 w% MDEA 140 73 19.7
Supplemental Mercaptan Removal
*K value derived from hydrocarbon mixture (benzene, toluene, ethyl benzene) If amine is used as the primary AGR process, and residual
organic sulfur species must be removed, it is possible to utilize
Based on data from RR-180 and RR-185

21-18
FIG. 21-18
Solubility Limit of Toluene in Amine Solutions
Liquid-Liquid Solubility Data and Model
Solubility Limit of Toluene in Amine Solutio
Liquid-Liquid Solubility Data and Model
10
10
Solubility Limit of Toluene (scf Vapor/Gallon Solution)

70
70 wt%
wt%DGA
DGA
Gall
/ 50
50 wt% MDEA
wt% MDEA
52.5
52.5wt%
wt%DGA
DGA
Vapor 1 46
46 wt%
wt%DGA
DGA
1 35 wt% DGA MDEA
35 wt% DGA DGA 50wt%
(scf 70wt% 25
wt% MDEA
25 wt% MDEA
5wt%DGA
52.
Toluene 14.6 wt% MEA
14.6 wt% MEA

DGA
46wt%
of 25wt%
MDEA

0.1 DGA
0.1 35wt%
Limit

MEA
14.6wt%

Solubility

0.01
0.01
50 70 90 110 130 150 170 190 210 230 250

Temperature
Temperature °F° Based on data from RR-206

FIG. 21-19
Change in Equilibrium Ratio with CO2 Loading
In 50 w% MDEA Solutions

60 3000

Benzene, 140 °F, 81 psia


Toluene, 140 °F, 65–89 psia
50 2500

Cyclohexane Equilibrium Ratio, K


Benzene or Toluene Equilibrium

40 2000
Cyclohexane, 140 °F, 73–83 psia
Ratio, K

30 1500

Benzene, 77 °F, ~75 psia


20 1000
Toluene, 77 °F, ~75 psia

10 500

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Based on data from RR-206


CO2 Loading (mole/mole MDEA)

21-19
large pore mole sieve (e.g., 13X) to accomplish organic sulfur Natural gas is usually water washed after a caustic wash
removal (ref. Clarke and Sibal).87 The regeneration system will to remove any caustic entrained in the gas prior to dehydra-
generate “spikes” in concentration of organic sulfur species, tion.
which must be managed in some way to avoid upsetting the
SRU. The chemical reactions involved are as follows:
H2S + NaOH → NaSH + H2O Eq 21-12
CAUSTIC WASH
NaSH + NaOH → Na2S + H2O Eq 21-13
Caustic (NaOH) scrubbing systems can be used to treat
natural gas streams to remove CO 2, CS2, H2S, and mercap- H2S + 2 NaOH → Na2S + 2H2O Eq 21-14
tans.29
RSH + NaOH → R SNa + H2O Eq 21-15
The process employs countercurrent contacting of the gas
stream with a caustic solution in a packed or trayed column
The column may contain one stage or several stages, de- CO2 + 2 NaOH → Na2CO3 + H2O Eq 21-16
pending on the required degree of removal. The multi-stage
systems generally have different caustic concentrations CS2 + 2 NaOH → 2 NaHS + CO2 Eq 21-17
ranging from 4–6 weight percent in the first stage to 8–10
A typical process flow diagram for a regenerative caustic
weight percent in the latter stages. Multiple stages increase
treating process is shown in Fig. 21-20. Physical property data
the caustic efficiency while maintaining a sufficient driving
for NaOH solutions that used to be provided in the GPSA Engi-
force to achieve absorption.30
neering Data Book have now been removed, but if required are
The spent solution is either regenerated or discarded de- available in the 12th Edition.
pending on what acid gas components are present in the gas
stream. If only mercaptans are present, the caustic solution Although caustic soda dissolves in water to form solutions of
is regenerated with steam in a stripping still. If CO2 is pres- high concentration, due account must be taken of the tempera-
ent, a nonregenerable product (Na 2CO3) is formed and the ture at which these solutions separate solid hydrates. A number
solution must be discarded. As a result, the presence of CO2 of these hydrates are formed which separate from solutions at
in caustic systems leads to high caustic consumption. This is definite temperatures and concentrations from –28 °C to 64.3 °C
a serious disadvantage of the caustic scrubbing process. The (–18.4 °F to 147.7 °F) and from 19% NaOH to about 74% NaOH.
spent caustic solutions are considered hazardous wastes.
The waste must be disposed of properly, since the reaction
can be reversed, and the H2S released if the waste is mixed
with other higher pH aqueous streams.

FIG. 21-20
Regenerative Caustic

21-20
PHYSICAL SOLVENT PROCESSES rosive so carbon steel can be used. Chemical losses are low due
to low solvent vapor pressure or refrigerated conditions. Physi-
These processes are based on physical absorption and oper- cal solvents will absorb heavy hydrocarbons from the gas
ate with a flow scheme as shown in Fig. 21-21. In general, a stream resulting in high hydrocarbon content in the acid gas
physical solvent process should be considered when:31 stream as well as possibly significant hydrocarbon losses.
 The partial pressure of the acid gas in the feed is greater Some of the physical absorption processes are summarized
than 50 psi below.
 The heavy hydrocarbon concentration in the feed gas is
low
Selexol®
This process developed by Allied Chemical Corp.32,33 uses a
 Bulk removal of the acid gas is desired
polyethylene glycol derivative as a solvent. The solvent is selec-
 Selective removal of H2S is desired tive for RSH, CS2, H2S, and other sulfur compounds. The pro-
cess can be used to selectively or simultaneously remove sulfur
 Organic sulfur removal such as mercaptan removal is compounds, carbon dioxide, water, as well as paraffinic, olefin-
desired ic, aromatic and chlorinated hydrocarbons from a gas or air
These processes are economically attractive because little stream. Because water and heavy hydrocarbons are highly sol-
energy is required for regeneration. The solvents are regener- uble in Selexol®, the treated gas from a Selexol ® unit normally
ated by: meets both water and hydrocarbon dew point specifications.
The vendor states that the solvent is very stable, no degrada-
 Multi-stage flashing to low pressures tion products are formed or disposed of, and no solvent reclaim-
ing is required. Depending on the applications, the operating
 Regeneration at low temperatures with an inert strip- pressure could be as low as ambient though higher pressure is
ping gas preferred. Operating temperature varies from 0 °F to ambient.
 Heating and stripping of solution with steam/solvent Selexol® is a UOP technology using a Union Carbide Corpora-
vapors tion (subsidiary of The Dow Chemical Company) solvent.
In general, physical solvents are capable of removing COS, Fluor Solvent
CS2, and mercaptans. In certain instances, physical absorption
processes are capable of simultaneously dehydrating and treat- This process patented by the Fluor Corporation, is based on
ing the gas although additional equipment and higher energy the use of anhydrous propylene carbonate.34 The temperature
requirements may be needed to dry the solvent. The processes of the lean solution to the absorber is usually well below ambi-
operate at ambient or subambient temperature to enhance the ent, and some method of refrigerating the solvent is usually
solubility of the acid gases. The solvents are relatively noncor- necessary.35

FIG. 21-21
Typical Gas Sweetening by Physical Absorption

Filtration

21-21
Rectisol Process® MDEA has higher capacity for CO2 absorption than DIPA.
However, the reaction kinetics with MDEA are slow. Sulfinol-
This process uses pure refrigerated methanol as a solvent X®, overcomes this drawback because of the accelerator. Since
and has been developed and licensed by Lurgi Oel Gas Chemie the CO2 absorption in Sulfinol-X is higher, this reduces solvent
and Linde. The process is often applied for syngas purification circulation by as much as 10% when compared to Sulfinol-D®.
and operates at temperatures as low as minus 30 to minus 100 °F. Because of the accelerated CO2 pickup, the absorbers are short-
Applications include selective or bulk removal of sour compo- er with Sulfinol-X® than with aqueous MDEA.
nents; however, the extremely low total sulfur impurities
achievable with this process (< 0.1 ppmv) are not normally re-
quired in natural gas treating applications. In the natural gas Solvent Characteristics
industry the process has been best suited for applications where Moderately fast reaction with CO 2, fast reaction
high concentrations of CO2 need to be removed. Sulfinol-D® with H2S. For complete removal of H2S, CO2 and
The process has also been used in the purification of natural other sulfur compounds.
gas for LNG production. However, since methanol co-absorbs Slow reaction with CO2. For selective removal of
higher hydrocarbons, implementation of the process has been Sulfinol-M®
H2S with partial removal of COS.
limited to applications where only low concentrations of C2+ hy- Fast reaction with CO2 and H2S. Higher CO2
drocarbons are present. absorption capacity than Sulfinol-D. For
®
Sulfinol-X
complete removal of H2S, CO2 and other sulfur
Ifpex-2 Process® compounds.
This process developed by IFP and licensed by Prosernat
uses refrigerated methanol solutions containing water in order All Sulfinol® formulations can reduce the total sulfur content
to reduce hydrocarbon co-absorption. It is generally associated of treated gas down to low ppm levels. Sulfinol® solvents can also
downstream of the Ifpex-1 dehydration process (see Section 20) remove aromatics, thus providing potential cost savings in down-
which simultaneously extracts heavier hydrocarbons. The If- stream processes like LNG and N2-rejection units.
pex-2 process attains equivalent acid gas and mercaptan re-
moval performance of the Rectisol process but at a slightly One disadvantage of the Sulfinol ® solvents is the higher
higher solvent rate due to the lower solvent purity.36 heavy hydrocarbon co-absorption. With Sulfinol-D®, a reclaimer
is sometimes required when removing CO 2. Since Sulfinol-M
Purisol® and Sulfinol-X contain MDEA in place of DIPA, a reclaimer is
not required as no DIPA-Oxazolidone is formed.
This process has been developed and licensed by Lurgi Oel
Gas Chemie.37 The solvent used is N-methyl-2-pyrrolidone Selefining Process
(NMP or N-Pyrol), a high boiling point liquid. Purisol exhibits a
selectivity for H2S, like Selexol, and features equivalent process This process developed by Snamprogetti (now part of
possibilities. Saipem) uses tertiary amines such as dimethyl ethanol amine
(DMEA) dissolved in an organic solvent with limited amounts
As Purisol is also well suited for the selective removal of of water. The process is very selective to H2S as CO2 hydration
mercaptans; it can be used for the recovery of mercaptans from is almost completely avoided. It also removes other sulfur spe-
regeneration off gases from adsorptive mercaptan removal cies such as mercaptans, COS and CS2. It has a tendency to co-
units. absorb hydrocarbons, which can to some extent be controlled by
increasing the water content of the solvent.
Morphysorb ®
This physical solvent process developed by Krupp Uhde ALKALINE SALT PROCESS
called Morphysorb38 uses a mixture of N-formyl morpholine (HOT CARBONATE)
(NFM) and N-acetylmorpholine as a physical solvent. The de-
veloper claims the process is best suited for processing gases The basic process was developed by the U.S. Bureau of
heavily loaded with acid components and entered commercial Mines and employs an aqueous solution of potassium carbonate
service in 2002. (K2CO3). The contactor and stripper both operate at tempera-
tures in the range of 230–240 °F . The process is not suitable for
HYBRID SOLVENT PROCESSES gas streams containing only H2S.11 If H2S is to be removed to
pipeline specification or there are low CO2 outlet specifications,
There are several gas treating processes which use the ef- special designs or a two-stage system may have to be used. Po-
fects of both physical and chemical solvents. One of the earlier tassium carbonate processes are somewhat effective in remov-
hybrid solvent processes developed by Lurgi was the Amisol ing carbonyl sulfide and carbon disulfide.
process combining amines with methanol. 39 Of the successfully
proven technologies in use today, the most widely used is The overall reactions for CO2 and H2S with potassium car-
Sulfinol®. bonate can be represented by:
K2CO3 + CO2 + H2O ↔ 2 KHCO3 Eq 21-18
Sulfinol® Process
K2CO3 + H2S ↔ KHS + KHCO3 Eq 21-19
The Sulfinol® Process, licensed by Shell Global Solutions, is
used to remove H2S, CO2, COS, CS2, mercaptans and polysul-
fides from natural and synthetic gases.40,41 Sulfinol® is a mix- There are three basic process variations for the potassium
ture of Sulfolane (a physical solvent), water and either DIPA or carbonate process. The flow scheme required depends on the
MDEA (with or without Piperazine, an accelerator). Both DIPA outlet specification of the natural gas. These are:
and MDEA are chemical solvents. It is this dual capacity as
both a physical and a chemical solvent that gives Sulfinol ® its
advantages.

21-22
Single Stage Process Numerous improvements have been made to the potassium
carbonate process resulting in significant reduction in capital
The single stage process is shown in Fig. 21-22. Potassium and operating costs. At the same time, lower acid gas concen-
carbonate is pumped to the top of a packed or trayed contactor tration in the treated gas can now be achieved. The most popu-
where it contacts the gas stream. The rich solution flows to the lar of the carbonate processes are:
stripper where the acid gases are stripped with steam. The lean
solution is then pumped back to the contactor to complete the Benfield® Process
cycle.
The Benfield® Process is licensed by UOP. Several activa-
Split Flow Process tors are used to enhance the performance of the potassium car-
bonate solution.
In this process scheme (Fig. 21-23) the lean solution stream
is split. Hot solution is fed to the middle of the contactor for Hi-Pure® Process
bulk removal. The remainder is cooled to improve equilibrium
and is fed to the top of the contactor for trim acid gas removal. The Hi-Pure® process is a combination of conventional Ben-
field® potassium carbonate process and an amine process. The
Two Stage Process gas stream is first contacted with potassium carbonate followed
by contacting with an amine. In this process it is critical to keep
In this process scheme (Fig. 21-24) the contactor is like that the downstream amine from being contaminated with the up-
of the split flow process. In addition, the stripper is in two sec- stream potassium carbonate solution. The process can achieve
tions. A major portion of the solution is removed at the midpoint outlet CO2 concentrations as low as 30 ppmv and H2S concen-
of the stripper and pumped to the lower section of the contactor. trations of 1 ppmv.42
The remainder is further stripped with steam and then cooled
prior to entering the top of the contactor. Catacarb® Process
The Catacarb® Process is licensed by Eickmeyer and Associ-
FIG. 21-22 ates. Activators, corrosion inhibitors, potassium salts, and wa-
ter are contained in the solution. This process is mostly used in
Alkaline Salt: Single-Stage Process
the ammonia industry.43

GENERAL CONSIDERATIONS FOR


SOLVENT PROCESSES
Solution Filtration
Filtration of the treating solution to remove entrained solids
is essential to the successful operation of a gas treating plant.
Filtration rates should be as high as practical and may range
from 5 per cent of circulation to full stream. Removing particles
down to 5 microns in size is recommended. In order to do this
efficiently, two stages of filtration may be required. The first
stage, typically a cartridge-type or precoat filter, is designed to
remove particles down to the 10 micron or less range. The sec-
ond stage of filtration, typically an activated carbon filter, re-
moves hydrocarbons and other contaminants. This is accom-
plished by adsorption. The activated carbon filter should always

FIG. 21-23 FIG. 21-24


Alkaline Salt: Split-Flow Process Alkaline Salt: Two-Stage Process

~
~
~
~

21-23
be located downstream of the first stage filter because the depo- In addition, many flash drum set-ups have a small absorp-
sition of solids would plug the carbon filter.44 tion column where a sidestream of the lean solvent is used to
wash the overhead vapor to partially reabsorb any flashed acid
The carryover of carbon fines can be controlled by either lo- gas. This is often used to ensure the acid gas contact of the va-
cating a second cartridge-type filter immediately downstream por is suitable for use as fuel gas.
of the carbon filter or using a graded carbon bed. In a graded
bed, larger granules are placed at the outlet of the filter to trap Vented Regenerator (Aromatics Impact)
fines. Large carbon granules produce fewer fines but are less
efficient for adsorption. If the acid gas is CO2 only and the regenerator off-gas is not
sent to a Claus Plant for sulfur recovery, then the level of aro-
Basic degradation products are identified by chromatogra- matics in the overhead need to be checked to determine wheth-
phy and mass spectrometry. Acidic degradation products are er it can be vented without using a thermal oxidizer to inciner-
identified by ion chromatography exclusion. These tests are rec- ate the hydrocarbons present.
ommended when the amine solution appears to lose its ability
to pick up acid gas. Degradation products affect the results of Corrosion
the conventional estimation of amine concentration by titra-
tion. This may cause artificially high or low apparent amine Corrosion is an operating concern in nearly all sweetening
concentrations Also, the carbon bed will adsorb very little installations. The combination of H2S and CO2 with water prac-
strong acid degradation products. In this case, purging or recla- tically ensures that corrosive conditions will exist in portions of
mation of the solution is recommended. the plant. In general, gas streams with high H 2S to CO2 ratios
are less corrosive than those having low H2S to CO2 ratios. H2S
Carbon filters can be partially regenerated with steam or concentrations in the ppmv range with CO2 concentrations of 2
hot steam condensate, which removes hydrocarbons and other percent or more tend to be particularly corrosive. Because the
adsorbed contaminants. Regeneration or bed change out is rec- corrosion in sweetening plants tends to be chemical in nature,
ommended when foam tests on the inlet and outlet streams it is strongly a function of temperature and liquid velocity. The
show no improvement. This indicates carbon bed saturation. type of sweetening solution being used and the concentration of
Filters should be located on the lean solution side in general that solution has a strong impact on the corrosion rate. In-
to avoid exposing personnel to hot rich solutions containing creased corrosion can be expected with stronger solutions and
H2S. However, filtration on the rich side may need to be done to higher gas loadings.
remove particles that are more insoluble under the rich solution Hydrogen sulfide dissociates in water to form a weak acid.
conditions. For such a situation it is mandatory, if H2S may be The acid attacks iron and forms insoluble iron sulfide. The iron
present (almost always at some level) that the design and oper- sulfide will adhere to the base metal and may provide some pro-
ating procedures reflect the need for personnel protection from tection from further corrosion, but it can be eroded away easily,
during filter maintenance. exposing fresh metal for further attack.
Filtration equipment should be used continuously begin- CO2 in the presence of free water will form carbonic acid.
ning with the first day of plant operations. When starting up The carbonic acid will attack iron to form a soluble iron bicar-
the plant, the full flow filter, even if temporary, may prove its bonate which, upon heating, will release CO2 and an insoluble
worth by removing the scale and other solid particles and allow- iron carbonate, or hydrolyze to iron oxide. If H2S is present, it
ing much quicker and easier start-up of the plant. will react with the iron oxide to form iron sulfide.
Flash Tank (Drum) High liquid velocities can erode the protective iron sulfide
film with resulting high corrosion rates. In general, design ve-
Rich solution leaving the contactor may pass through a flash locities in rich solution piping should be 50% of those that would
tank. A flash tank is more important when treating high pres- be used in sweet service. Because of the temperature relation-
sure gas. First, the drum will separate entrained gases in the ship to corrosion, the reboiler, the rich side of the amine-amine
rich solution leaving the absorber. Second, the amount of ab- exchanger, tend to experience high corrosion rates. Because of
sorbed gas will decrease, because of the lower operating pres- the low pH the stripper overhead condensing loop also tends to
sure of the flash tank. Using a flash tank will: experience high corrosion rates.
 Reduce erosion in rich/lean exchangers Solvent degradation products also contribute to corrosion. A
 Minimize the hydrocarbon content in the acid gas suggested mechanism for corrosion is that degradation prod-
ucts act as chelating agents for iron when hot. When cooled, the
 Reduce the vapor load on the stripper iron chelates become unstable, releasing the iron to form iron
sulfide in the presence of H2S. Primary amines are thought to
 Possibly allow the off-gas from the flash tank to be used
be more corrosive than secondary amines because the degrada-
as fuel (may require sweetening)
tion products of the primary amines act as stronger chelating
When heavy hydrocarbons are present in the natural gas, agents.
the flash tank can also be used to skim off the heavy hydrocar-
Several forms of stress corrosion cracking are possible in
bons that were absorbed by the solution. Residence times for
amine sweetening systems. Amine stress corrosion cracking
flash tanks in amine service are often designed with up to 10+
can occur and is worse in hot solutions, but cracking can occur
minutes for the liquid phase depending on separation require-
in cooler lines and both rich and lean streams. Post-weld heat
ments. Inlet gas streams containing only methane and ethane
treatment (PWHT) can prevent this type of cracking45. Wet sul-
require shorter residence times. Rich gas streams require lon-
fide cracking and blistering can occur due to hydrogen gener-
ger time for the dissociation of gas from solution and/or the
ated in corrosion reactions. The hydrogen can collect at small
separation of liquid phases.
inclusions in the steel which delaminate and then link in a step-

21-24
wise pattern to create blisters. This is called HIC or hydrogen  Organic acids
induced cracking. Sometimes stress influences the cracking to
cause stress oriented hydrogen induced cracking (SOHIC).  Corrosion inhibitors
PWHT helps, but does not prevent HIC and SOHIC. HIC resis-  Condensed hydrocarbons
tant steels are available. Seamless pipe is less prone to HIC
than plate steels.  Soap-based valve greases

Corrosion in alkaline salt processes, such as the hot carbon-  Makeup water impurities
ate process, has been reported to range from none to severe.  Degradation products
Corrosion can be expected where CO2 and steam are released
through flashing. Severe erosion can take place when carbonate  Lube Oil
solution strengths exceed 40% because of the tendency to form
bicarbonate crystals when the solution cools.  Too much anti-foam

Many corrosion problems may be solved using corrosion in- Foaming problems can usually be traced to plant operation-
hibitors in combination with operating practices which reduce al problems. Contaminants from upstream operations can be
corrosion. Following are some guidelines to minimize corrosion. minimized through adequate inlet separation. Condensation of
hydrocarbons in the contactor can usually be avoided by main-
 Maintain the lowest possible reboiler temperature. taining the lean solution temperature at least 10 °F above the
hydrocarbon dew point temperature of the outlet gas.
 If available, use low temperature heat medium rather
than a high temperature heat medium or direct firing. Temporary upsets can be controlled by the addition of anti-
When a high temperature heat medium or direct firing foam chemicals. These antifoams are usually of the silicone or
for the reboiler is used, caution should be taken to add long-chain alcohol type.
only enough heat for stripping the solution.
The following test for foaming should be run with the vari-
 Minimize solids and degradation products in the system ous types of anti-foam agents being considered for a given ap-
through reclaimer operation and effective filtration. plication.46 This test should give the operator an indication of
which antifoam will be the most effective for the particular
 Keep oxygen out of the system by providing a gas blanket case. Place several drops of antifoam in 200 ml of treating solu-
on all storage tanks and maintain a positive pressure on tion contained in a 1000 ml cylinder. Bubble oil-free air through
the suction of all pumps. the solution at a constant rate. After five minutes have elapsed
 Ensure deionized water or oxygen/chemical-free boiler shut off the air and start a timer. Note the height of foam at the
condensate is used for make up water. If available, steam time the air was shut off and the amount of time required for
can be used to replace water loss. the foam to break. The foam height is the difference between
the height of the foam and the initial height of the liquid. The
 Limit solution strengths to minimum levels required for time for the foam to break is an indication of the stability of the
treating. foam. A comparison of antifoams will let the operator select
which chemical will best solve their foaming problems. Between
 Pipe solution exchangers for upflow operation with the
anti-foam tests, care should be taken to clean the test cylinder
rich solution on the tube side.
thoroughly, because a very small amount of the prior anti-foam
 Monitor corrosion rates with coupons or suitable corro- used may affect the test.
sion probes.
Materials
 Maintain adequate solution level above reboiler tube
bundles and fire tubes; a minimum tube submergence of Treating plants normally use carbon steel as the principal
12 in. is recommended. material of construction. Vessels and piping should be stress
relieved in order to minimize stress corrosion along weld seams.
Corrosion inhibitors used include high molecular weight Corrosion allowance for equipment ranges from 1/16 in. to 1/4
amines and heavy metal salts. The compositions are generally in., typically 1/8 in. In some instances, when corrosion is known
proprietary. Certain inhibitors can only be used when only H2S to be a problem, or high solution loadings are required, stain-
or CO2 is in the gas, which allows increased solution strengths less steel or clad stainless steel may be used in the following
and acid gas loadings. These inhibitors offer potential savings critical areas:
in both capital and operating costs for these special cases. An
example of this type of inhibitor use is in ammonia plants.  Reflux condenser

Foaming  Reboiler tube bundle

A sudden increase in differential pressure across a contactor  Rich/lean exchanger tubes


or a sudden liquid level variation at the bottom of the contactor  Bubbling area of the contactor and/or stripper trays
often indicates severe foaming. When foaming occurs, there is
improper contact between the gas and the chemical solution,  Rich solution piping from the rich/lean exchanger to the
liquid hold-up increases and if uncontrolled will result in liquid stripper
carryover from the contactor. The result is reduced treating ca-  Bottom 5 trays of the contactor and top 5 trays of strip-
pacity and sweetening efficiency, possibly to the point that out- per, if not all
let specification cannot be met.
Usually 304, 316, or 410 stainless steel will be used in these
Some reasons for foaming are: 13 areas, even through corrosion has been experienced with 410
 Suspended solids stainless in DEA service for CO2 removal in the absence of H2S.
L grades are recommended if the alloys are to be welded.

21-25
Controlling oxygen content to less than 0.2 ppmw is effec- Iron-sponge process — Iron sponge processes have been
tive in preventing chloride SCC in waters with up to 1000 ppmw used in the industry for decades. They selectively remove H2S
chloride content, at temperatures up to 570 °F. There has been from gas or liquid streams. The process is limited to treating
an increased use of duplex stainless steels, and they have been streams containing low concentrations of H2S at pressures rang-
successfully used in the water treatment industry to prevent ing from 25 to 1200 psig. The process employs hydrated iron
chloride SCC in high chloride waters. This suggests duplex oxide, impregnated on wood chips.
stainless steels could be utilized in amine plant service where
Care must be taken with the iron sponge bed to maintain
high chloride content is expected. As with any specialty steel,
pH, gas temperature, and moisture content to prevent loss of
proper fabrication techniques and welding procedures are
bed activity. Consequently, injections of water and sodium car-
required. bonate are sometimes needed. H2S reacts with iron oxide to
form iron sulfide and water. When the iron oxide is consumed,
BATCH AND CYCLIC PROCESSES the bed must be changed out or regenerated. The bed can be
regenerated with air; however, only about 60% of the previous
In this section, processes having chemical reactions and/or
bed life can be expected.49 The bed life of the batch process is
physical adsorption are discussed. They all have the common
dependent upon the quantity of H2S, the amount of iron oxide in
requirement that the process be operated as a batch or cyclic
the bed, residence time, pH, moisture content, and
system. At the end of the cycle the operator must either change
temperature.
solution or regenerate in order to continue treating.
Under this heading the following process classification is The change-out of the spent sponge beds is hazardous. Iron
considered: sulfide is pyrophoric, and when exposed to air will rapidly oxi-
dize, and can result in spontaneous combustion of the spent bed.
 Scavenger processes with liquid or solid sacrificial scav- To prevent this, the entire bed should be wetted before begin-
enging agents ning the change-out operation. Regulations on sponge disposal
vary with location; therefore, local regulations on allowable
 Adsorption processes both non-regenerable like activated methods of disposal should be checked.
carbon and cyclically regenerated adsorbents such as mo-
lecular sieves Sulfa-Check ® — Sulfa-Check® is a product from Nalco,
which selectively removes H2S and mercaptans from natural
Scavenger Processes gas in the presence of CO2. The process converts the sour gas
directly to sulfur. This is accomplished by sparging the gas in a
Scavengers are chemicals which react with H2S and some-
buffered, water-based oxidizing solution containing sodium ni-
times other sulfur compounds like COS or mercaptans. Gener-
trite (NaNO2). The sodium nitrite is reduced to ammonia (NH3),
ally the spent product is not or cannot be regenerated so the use which remains in solution. The spent product is classified as
of scavengers is limited to the removal of small quantities of
non-hazardous.
sulfur impurities.
This process is suitable for ranges from 15 Mscf/d to 3.0
Scavengers can be applied in a continuous or batch mode. In MMscf/d and inlet H2S ranging from 10 ppmv to 3000 ppmv.50
the continuous mode the liquid scavenger is injected into the
gas stream after separation of liquid hydrocarbons and water. A number of variables, including some associated risks,
After introducing the scavenger via a quill or spray nozzle, or in must be considered prior to determining if the Sulfa-Check®
some cases using a static mixer, and although the chemical re- process is applicable. For example, low levels of ammonia may
action is very fast, a sufficient length of pipe must be provided appear in the treated gas. Also, the reduction of NO2 may result
to allow mass transfer into the liquid to occur. The nature of the in the formation of nitric oxide (NO). If air is present in the raw
two phase flow regime, i.e., whether entrained flow (which is gas, it will react with the nitric oxide, to form nitrogen dioxide
preferred) or stratified flow is present is critical. The mixture is (NO2). NO2 is a strong oxidizing agent that will react with elas-
then separated in a coalescing filter and the resultant liquid tomers and odorants, and cause corrosion in a moist environ-
product is discarded. ment. It is recommended that Nalco be contacted for further
information.
In the batch mode the gas is passed through a vessel filled
with liquid or solid scavenger agent. The batch mode has a SulfaTreat® — SulfaTreat® is an H2S scavenging process
higher scavenger utilization efficiency, especially if a lead lag offered by MI-Swaco. The material is a dry, free-flowing, granu-
configuration is used, but a much higher capital cost. In the lar substance used for selective removal of H 2S from natural gas
case of liquids overtreating the liquid scavenger can result in in the presence of CO2. The process is not affected by CO 2, and
sludge material forming in the tower exacerbating the difficul- it does not produce elemental sulfur or nitric oxides. Also Sulfa-
ties involved during changeout. Treat® will not ignite in the vessel. Other advantages include
longer bed life and lower cost relative to the iron sponge process.
Typical batch changeout periods might be on the order of The capacity is adversely affected, if the gas is too far below
every 30 days. Too much longer than this and the size becomes water saturation.
prohibitive and too much shorter the cost of changeout opera-
tions becomes too high. Batch tower net costs might approach Applications for SulfaTreat® include: natural gas treating,
$30,000 per lb of sulfur removed. amine treater off gas, high concentration CO2 streams, and any
other H2S-containing gases.
The rest of this section provides information on some of the
more common scavenger processes employed in gas processing MI-Swaco also offers other SulfaTreat® absorbents besides
services. Computer programs are available to estimate capital the original SulfaTreat® product for removing H2S and mercap-
and operating costs of batch scavenger & liquid scavenger injec- tans from hydrocarbon gas & liquid streams.
tion applications.47,48 ®
Puraspec — Johnson Matthey Catalysts supplies the
Puraspec® range of processes and products for desulfurisation of

21-26
hydrocarbon gases and liquids. The processes use fixed beds of SULFURTRAP® will yield an outlet concentration of <1 ppm
granular, metal oxide-based chemical absorbents, which are de- H2S until bed change out is required.
velopments of the ‘high temperature zinc oxide’ used for purifi-
cation of hydrocarbon feedstocks to steam reformers in ammo- Liquid triazine based scavengers — Most liquid scaven-
nia, hydrogen, and methanol plants. Puraspec® absorbents are gers are ethanol triazines, but some methanol triazines are also
effective at temperatures down to 32 °F, so no added heat is in use. The active ingredient for ethanol triazine formulations
necessary, and are in service at pressures from atmospheric is usually 1,3,5 tris (2-hydroxyethyl)-hexahydro-1,3,5 triazine,
(treating vent gases) to 1800 psia treating dense phase gas feed but it is sold diluted to various degrees, but usually around
to a gas processing plant. 50%, by water. The exact ingredients of the commercial scaven-
gers are often proprietary and difficult to determine, however.
Puraspec® units are in service treating natural gas to pipe- A typical capacity range, as directly observed in batch applica-
line or petrochemical specifications.51,52 Because the absorbents tion in the field, was 0.5 to 0.8 lb S removed per gallon of scav-
remove H2S and COS irreversibly, they are best suited to pol- enger for a 50% solution of triazine in water. Ultimately, what
ishing duties. In large scale applications this can be removal of is important is not the price of the scavenger per unit volume,
up to 50 ppmv or 200-400 lbs per day of sulfur. Liquid treating as it is commonly sold nor the capacity per gallon, but rather
applications include removal of H2S/COS from LPG to meet cop- the amount of H2S which can be removed for a given cost of
per strip test specifications. Spent absorbents are normally sent scavenger. It may require experimentation to determine the
to metals refineries where they can be treated as high-grade most cost effective product.
ores for metals recovery.
There are many manufacturers for these products and the
SULFURTRAP®— Chemical Products Industries, Inc pro- product names change frequently, so it is hard to provide an
vides this patented H2S absorbent/catalyst and process, which accurate list in this book. Some of the current manufacturers of
uses a dry, free-flowing, spherical material for selective remov- these products include Baker Petrolite, Clariant, Nalco, MI-
al of hydrogen sulfide (H2S) and light mercaptans from natural Swaco, Swan Industries, Champion Technologies, Quaker
gas & NGLs. SULFURTRAP® is environmentally non-hazard- Chemicals, Edmunds and Assocates and BetzDearborn.
ous, is not affected by CO2, and does not need the addition of
water vapor to function properly. SULFURTRAP® is capable of Liquid polyols — A new alternative for H2S and light mer-
high sulfur loading capacities resulting in long bed life, is non- captan scavenging is based on a hydroxyl stabilized polyol. Re-
pyrophoric and it will not agglomerate or cake in its reacted moval is quasi-instantaneous and the chemical reaction is irre-
(spent) form allowing easier change out and disposal. versible. The scavenger is water-based and its activity can be
customized based on its concentration. Typical capacity ranges
SULFURTRAP ® is applicable for H2S removal applications from 1.2 to 1.5 lb of H2S per gallon of product. The precise ingre-
up to 0.5 TPD sulfur. Regardless of inlet H2S concentration, dients and chemical composition are proprietary and difficult to

FIG. 21-25
Integrated Natural Gas Desulfurization

21-27
determine; however, it contains no nitrogen, no heavy metals The redox agent is then regenerated by reaction with air in
and no aldehydes. Exact dosage for this scavenger needs to be an oxidizer vessel.
tested and adjusted based on removal specifications. Compa-
nies such as Nexo Solutions, No Heat resources and Exion sys- Liquid redox sulfur recovery processes all share the follow-
tems have this product available. ing major steps:55
 Sour gas cleaning by absorption of H2S into a circulating
Adsorption Processes alkaline solution
Adsorption is also used to remove H2S, CO2 and other sulfur  Conversion of the formed HS to elemental sulfur via the
contaminants from natural gases. Adsorbents used are either action of an auxiliary redox reagent (ARR)
regenerated such as molecular sieves or not regenerated such
as impregnated activated carbon.  Separation and recovery of solid sulfur
Molecular sieve — Molecular sieves can be used for re-  Regeneration of the spent auxiliary reagent via reaction
moval of sulfur compounds from gas streams (Fig. 21-25). Hy- with oxygen dissolved in the solution
drogen sulfide can be selectively removed to meet 0.25 grain/100
The processes share the general chemistry shown below. 55
scf specification. The sieve bed can be designed to dehydrate
and sweeten simultaneously. In addition, molecular sieve pro-  H2S absorption using an alkaline solution:
cesses can be used for CO2 removal. HS↔HS Eq 21-21
2 (g) 2 (sol’n)
In general, the concentrations of acid gas are such that cycle
times are in the order of 6–8 hours. It is possible to do CO2 H2S(sol’n) ↔ H+ + HS– Eq 21-22
removal on shorter cycles using multiple beds. However, the Note that this is a non-selective, basic scrubbing solution;
system must be designed accordingly. To operate properly, thus, additional acidic components (CO2 , HCN) of the sour gas
the sieves must be regenerated at a temperature close to 600 °F will be soluble in the scrubbing solution. While CO2 is partially
for a long enough period of time to remove all adsorbed materi- absorbed in the alkaline solution, it does not participate in the
als, usually one hour or more. Exact arrangement of the regen- redox reactions. CO2 may however increase the rate of con-
eration cycle depends upon process conditions. sumption of caustic or buffering compounds. The fate of other
Regeneration of a molecular sieve bed concentrates the H2S reduced sulfur species (COS, CS2, RSH, RSR) depends on the
into a small regeneration stream which must be treated or dis- particular process being considered.
posed of. During the regeneration cycle, the H2S will exhibit a  Conversion to Elemental Sulfur:
peak concentration in the regeneration gas. The peak is ap-
proximately 30 times the concentration of the H2S in the inlet HS– + H+ + 12O2(sol’n) → H2O(1) + 18S8 Eq 21-23
stream. Knowing the concentration of this stream is essential
for the design of a gas treater for the regeneration gas. Note that, in the absence of an auxiliary redox reagent
(ARR), the reaction shown as Equation 21-23 is slow and non-
The problem of COS formation during processing according specific. The addition of an ARR increases the rate of reaction
to the reaction: and directs the oxidation to elemental sulfur. The reaction
H2S + CO2 ↔ COS + H2O Eq 21-20 shown as Equation 21-24 is common to all the processes consid-
ered in this section.
has been extensively studied. Molecular sieve products have
been developed that do not catalyze COS formation.53 The cen- HS– + ARR(OX) → 18 S8 + H+ + AAR(RED) Eq 21-24
tral zone in the regeneration cycle is most favorable to COS where (OX) denotes the oxidized form and (RED) denotes the
formation. reduced form of the ARR.
Operation of adsorbent plants is simple, but design is com-
plex. For example a dust filter is generally required down- Regeneration of the Spent ARR Using Air:
stream of the beds to ensure that fine solid particles are not
entrained into the treated gas. Manufacturers must be consult- O2(g) ↔ O2(sol’n) Eq 21-25
ed for potential applications. Refer to Dehydration (Section 20) ARR(RED) + O2 (sol’n) + 2 H → ARR(OX) + H2O(1) Eq 21-26
2
1 +

and the gasoline and LPG treating portion of this section for
additional details.
Oxorbon — Oxorbon is an alternative solid bed material The overall simplified chemistry of liquid redox processes is
which consists of activated carbon impregnated with potassium thus:
iodide (KI). Donau Carbon markets such a carbon for the re- H2S(g) + 1 O2(g) → H2O(1) + 1 S8 Eq 21-27
moval of H2S and mercaptans. The adsorbed H2S is converted to 2

elemental sulfur by catalytic reaction under the presence of


oxygen. The resulting sulfur is fixed on the pores of the acti-
Because they share major process operations and are based
vated carbon. Sulfur loadings as high as 60% of the carbon mass
on similar process chemistries, the process flow sheets and
have been reported and sulfide concentrations below 1 ppmv
equipment requirements for liquid redox systems are rather
are claimed.
similar.
LIQUID REDOX PROCESSES Stretford Process
Processes in this group absorb H2S from gas streams and The Stretford process was developed by British Gas PLC. It
produce elemental sulfur by reacting oxidizing/reducing agents involves the use of vanadium salts as the ARR. The process has
with the H2S to form elemental sulfur and water.54 been extensively used in Europe,54 however, environmental

21-28
concerns around the discharge of vanadium compounds has tal costs. The optimum application for SulFerox® is in the one to
limited its use. twenty tons per day range of recovered sulfur.

Iron Chelate Processes Sulfint-HP®


Currently, chelates are the most commonly used auxiliary The Sulfint-HP® process is another iron-chelate based liquid
redox reagents (ARR). A chelating agent is generally an organic redox technology licensed by Prosernat. It is claimed that it can
molecule which is able to bind with a metallic cation in such a be directly applied to high pressure sour gas streams. To avoid
way that the cation is sequestered from the solution. To illus- the problems of sulfur plugging at elevated pressure, Sulfint-
trate, consider the case of iron compounds. Fe(III) is capable of HP® applies direct filtration to the sulfur containing solution,
oxidizing H2S to sulfur, with subsequent formation of Fe(II). which exits the high-pressure absorber.60 After filtration, the
Fe(II) is easily oxidized by air back to Fe(III). However, both clarified high pressure solution can then be partly recycled back
forms of unsequestered iron will form precipitates with the sul- to the absorber, thus minimizing the pumping cost, while the
fides or oxides in solution, thereby rendering them ineffective. other portion is letdown in pressure to be regenerated with air
By chelating the iron with a compound like ethylenediaminetet- in an oxidizer vessel. The expansion of the aqueous-based redox
raacetic acid (EDTA), the iron will not precipitate, but is still solution yields extremely low amounts of flashed gas. Sulfint-
able to transfer an electron in the redox process. The process HP® process operation has proved easy and reliable in field
solutions are monitored regularly with occasional addition of operation.61
buffering agents, and sometimes defoamers, being required.
A common problem with chelate-based processes is the deg- LIQUID PHASE CLAUS REACTION
radation of the chelating agent.56 Another problem is sulfur PROCESSES
plugging in the contact tower. For this reason, these processes
were usually limited to low pressures (below 300 psig), unless CrystaSulf, marketed by CrystaTech, Inc., is a technology
combined with a high pressure amine absorber. Today direct that utilizes a non-aqueous solution to absorb H2S from the pro-
applications to high pressure sour gases have been developed cess stream, and react it with dissolved SO2 to form elemental
and these are mentioned hereafter. sulfur via the Claus reaction.62 The proprietary non-aqueous
solution does not absorb CO2, and therefore is not affected by
Because they share major process operations and are based high partial pressures of CO2.
on similar process chemistries, the process flow sheets and
equipment requirements for liquid redox systems are rather After contact with the process stream, the solution is flashed
similar. Lo-Cat, SulFerox, and Sulfint-HP are chelated iron liq- to lower pressure. The sour flash gas is usually vented to flare,
uid redox processes. but may be compressed and returned to the inlet, if desired. The
solution keeps elemental sulfur dissolved until the temperature
Lo-Cat II® is reduced in the crystallizer. There, elemental sulfur precipi-
tates from solution. The problem of sulfur plugging in high-
The Lo-Cat II® process,57,58,59 licensed by Merichem, is an pressure equipment is thus avoided, and the process can be ap-
improvement over the earlier Lo-Cat® process. The process can plied to high-pressure gas streams.
be applied directly to natural gas sweetening or treatment of
low-H2S acid gas for conversion of H2S to sulfur (see Section 22). This alternative to liquid redox processes has recently been
The process uses a solution of iron which is held in solution by commercialized.63
organic chelating agents. The iron in the solution oxidizes the
hydrogen sulfide to sulfur. The solution is then circulated to an BIOLOGICAL PROCESSES
oxidizer and regenerated for reuse in the process.
Among biological processes worthy to mention is the THI-
The process will not remove CO2, COS, CS2 nor RSH. If de- OPAQ® process commercialized by Paques in the early 1990s for
sired, some CO2 can be removed from the feed gas by strong low pressure gas desulpherization. Subsequently, Paques and
buffering of the solution. High pH has a negative impact on Shell Global Solutions developed the ShellPaques process for
sulfur conversion in LoCat solution, therefore the pH needs to H2S removal from higher pressure gas streams with the first
be maintained at the correct level. At high CO2 partial pres- commercial unit starting up in 2002. The Shell-Paques process
sures (above 30 psi), the requirement to maintain pH control can be considered for removing H2S in the form of bio-sulphur
can become a significant design issue. for applications up to 15 long tons per day.
Lo-Cat II utilizes special additives to reduce the rate of chel- In this process a gas stream containing H 2S contacts an
ant degradation. For acid gas applications, an auto-circulation aqueous soda solution containing sulfur bacteria in an absorb-
design is offered. Here, sparging of air in the oxidizer box causes er. The soda absorbs the H2S and then flows to a regenerator.
solution to flow to the next compartment, obviating the need for The regenerator consists of an aerated atmospheric tank where
a pump. The sulfur derived from the process may be suitable for hydrogen sulfide is biologically converted to sulfur. The sulfur
sale as a soil amendment. may be recovered as a moist filter cake or as a liquid product.

SulFerox® MEMBRANE SEPARATION PROCESS


The Shell SulFerox® process, developed by Shell and the Membranes are thin, polymer-based barriers that allow
Dow Chemical Company, is also an iron chelate redox technol- preferential passage of certain substances over others. 64 Gas
ogy that removes hydrogen sulfide and converts it directly to separation through membranes relies on the principle that gas-
salable sulfur in one step. The process offers low capital and es dissolve in and diffuse through membrane polymers. Certain
operating costs through the use of a high concentration iron gases like H2O, H2S, and CO2 will permeate through a mem-
chelate solution and effective control of chelate degradation. brane at a faster rate than hydrocarbons due to differences in
The process also offers a patented contactor design to improve diffusivity and solubility of those gases through that membrane
the overall efficiency of the process which further reduces capi-

21-29
as shown in Fig. 21-26. The difference in gas permeability rates the CO2 content of the gas to be treated is high (over 10%). Still,
through the membrane provides the basis for the separation. project specific requirements sometimes allow membranes to be
The separation is driven by the component partial pressure dif- economically attractive even at CO2 levels as low as 2%, for ex-
ferences across the polymer membrane. ample when the gas is already dehydrated, so that an addition-
al dehydration step can be avoided. Although the highest H2S
Therefore the technology is effective for bulk removal of partial pressures of an operating unit as of 2010 is only 20 psi,
CO2 and H2S and is less applicable for very stringent sour gas membranes could in future become attractive for bulk removal
specifications. They are very attractive for use where there is a of H2S in highly sour service. Bench testing indicates that at
final sweetening process like an amine unit or a H 2S polishing least one of the currently available membranes has no practical
bed available downstream. However, if the inlet sour gas has maximum H2S partial pressure limit.
already been dehydrated, membranes can be attractive for
meeting CO2 product specifications down to 2% CO2 in some Other benefits of membrane systems are: a lower capital in-
applications. vestment than amine plants in most cases, reduced maintenance
and labor costs, no moving parts (unless recycle compression is
FIG. 21-26
needed to recover hydrocarbons), no chemical consumption, flex-
Typical Relative Cellulose Acetate Membrane ibility in adjusting to variations in feed flow and feed composi-
Permeabilities (Courtesy UOP, A Honeywell Company) tion, and a significant space and weight advantage over amine
plants. The last benefit is particularly significant in offshore
Rel. Per. applications.
H2O 100 The table provides typical selectivity numbers to highlight
He/H2 30 where membrane separation can be used effectively. The actual
membrane properties can be highly dependent on pressure,
H2S 15 temperature, flow and composition. It is recommended to check
CO2 12 with the membrane supplier for proper evaluation.

CS2 7 Highly Sour Gas Pretreatment Processes


COS 2 If the acid gas content is over 15% then another class of pro-
CO 1 cesses, in addition to those relying on a physical solvent should
be considered where distillation of the acid gases from the sour
Nitrogen 1 gas is used in the process scheme to reduce the load on or in
Methane 1 some cases eliminate the solvent.

Ethane 1/3 SPREX®


Propane 1/10 In the Sprex® process developed by IFP with Total and mar-
Butane 1/15 keted by Prosernat66 a substantial part of the acid gases; nota-
bly the H2S, from the inlet gas is pre-extracted in a cyclone or
Pentane 1/20 column with a cold reflux from a downstream cold box. The acid
Hexane 1/25 gas is separated as a pumpable liquid at line pressure and am-
bient temperature. A demonstration plant was built and start-
ed up in 2005 to commercialize the technology.
In the design of membrane systems for these purposes it is Bulk Fractionation
important to focus on achieving high selectivity of CO2 vs. natu-
ral gas in order to avoid natural gas losses. To maximize the Another technique that can be employed is bulk fraction-
hydrocarbon recovery, recycling and reprocessing of the perme- ation or distillation of acid gases from the inlet feed. As dis-
ate gas is often required to avoid prohibitive natural gas losses. cussed in Section 16 direct distillation of the CO 2 from the inlet
In all membrane systems proper pre-conditioning of the inlet natural gas is limited by the CO2 solidification zone to about 15
gas is critical to avoid premature membrane deactivation. Se- mol% CO2 in the product gas.
lecting the right membrane pretreatment is the key to maxi-
Further treatment of the residue gas requires an additional
mize lifetime of the membrane material employed.65
processing step to meet typical sales gas specifications or the
Several large membrane systems, including some treating use of a solidification suppression additive (Ryan/Holmes Pro-
over 500 MMscfd of gas containing over 30 mol% CO2 have been cess) as described in Section 16 or the use of the CFZ ® being
successfully implemented as a result of advances in pretreat- commercialized by ExxonMobil (See Emerging Technologies).
ment technology.
Natural gas sweetening (particularly CO2) and dehydration PROCESS SELECTION
using membranes often offer significant advantages over the Selection of the best technology to apply to a given gas
more conventional methods such as amine treating, physical stream depends on many factors, and should be done by expe-
solvents, and solid adsorbents. Membranes can be used by rienced personnel. Among the factors to be considered are: feed
themselves or in conjunction with amine units to maximize the temperature and pressure, type and concentration of impuri-
benefits of both technologies. To minimize plasticization of ties, desired gas specification, flow rate, location, operating ex-
membrane materials, the CO2 partial pressures are limited to pense, and overall cost. Despite the large number of parameters
approximately 600 psi. Membranes are particularly attractive involved, it is possible to give some general guidelines as to
when the pressure of the feed gas is high (over 500 psig) and/or which process is most appropriate. For example, physical sol-
vents will generally be more attractive than chemical solvents

21-30
FIG. 21-27
Process Selection Chart for Simultaneous Removal of H2S and CO231

when the partial pressure of acidic components is high, owing to try. However, much more emphasis is given to minimize size
the higher loading and lower regeneration energy requirements and weight of the equipment. For floating production certain
associated with a physical solvent. If heavy hydrocarbons are precautions also need to be taken in order to mitigate the nega-
present, however, physical solvents may be less attractive due tive influences of the vessel movements. Of particular impor-
to their tendency to co-adsorb these contaminants. tance is the constant tilt of any contacting and regeneration
towers, which will seriously deteriorate the performance of the
Fig. 21-27 shows an example solvent process selection chart
towers due to mal-distribution. References are made to Sections
for the case where both H2S and CO2 are to be removed from the
7 and 19, where the separators and fractionators /absorbers
gas stream. This is a modified version of a graph taken from
face similar challenges.
Tennyson and Schaaf31 who also presented cases for removal of
only H2S, only CO2, and selective H2S removal. Note that spe- Some key considerations of importance for a sound design of
cific conditions may dictate the use of a process different from a hydrocarbon treating system on an offshore installation are:
what is presented in this type of chart. 67
 Use of sophisticated high tensile strength metallurgy,
since this will both reduce equipment weight and allow
ACID GAS INJECTION for less maintenance. The reduced equipment weight is
In some cases, it is possible to compress the acid gas as gen- due to reduced wall thickness when using high tensile
erated from a chemical or a physical solvent process and inject steels.
it into a depleted, non-producing, or even a producing reser-  Use of compact contacting technology in order to save
voir.68 A key consideration is the phase behavior of the acid gas weight and space
mixture. Depending on temperature, pressure, and composi-
tion, the acid gas may be injected as a liquid or gas; or as a  Use of compact module-based units with great emphasis
dense phase. Dehydration is usually necessary to avoid corro- on optimized piping lay-outs and integrated solutions in
sion or hydrate formation. However, in many cases, a minimum order to save weight and space
in water-holding capacity occurs with respect to pressure Thus,
 Emphasis on keeping a clean operating plant by:
it may be possible to compress the gas to a given level, cool it,
and drop out the liquid water. Further compression increases  Starting with a clean plant and degreasing before
the capacity of acid gas to hold water, so that water drop out first fill and after large revamps
should not occur in the downstream piping or well. The phase
behavior of acid gas mixtures is complex, and careful consider-  Keeping the feed gas clean by proper pretreatment
ation must be given to the design of the project.69,70  Maintaining a clean solvent by proper solvent filtra-
There have been a number of successful acid gas injection tion with both charcoal and mechanical filters and
projects, with sulfur contents from as little as 1 to more than minimizing use of additives like anti foam agents
1500 tons per day.71  Keeping a clean system by avoiding hydrocarbon
condensation in the absorber by superheating the
OFFSHORE DESIGN CONSIDERATIONS feed, if retrograde properties exist, insulating the
contactor, and/or keeping a safe differential temper-
Hydrocarbon Treating in the offshore industry encompasses ature between liquid inlet and gas inlet (typically 20
many of the same processes as can be seen in the onshore indus-

21-31
°F higher on liquid side). While desirable onshore, Controlled-Freeze Zone® (CFZ®) Process
keeping a clean operating plant is much more impor-
tant offshore, because of the great difficulties of This ExxonMobil process removes CO2, H2S, and other im-
“trucking” in huge reclaiming equipment and other purities from natural gas. The unique aspect of the process is
remediative equipment.81 that it induces CO2 freezing in an open area of a cryogenic frac-
tionation column.83 (The Ryan Holmes process, described in
 Well equipped offshore laboratory with skilled per- Section 16, adds a hydrocarbon stream to suppress CO2 freezing
sonnel is very important, since there is more incen- in the distillation column.) The solid CO2 melts in the stripping
tive for problems that require troubleshooting to be section of the CFZ column, and flows out as a liquid along with
solved on-site the other contaminants. The liquid stream can then be easily
pumped for downhole disposal. Methane, nitrogen, and helium
 Special considerations for floating production units
come out overhead.
should include:
 Avoiding constant tilt greater than 1 degree CryoCell® Process
 Keeping vessel movements to a minimum with This process83 offered by Cool Energy is a new technology for
full dampening often required the removal of CO2 from CO2 rich feed gases. In the process de-
hydrated feed gas is cooled to a temperature just above the
 Careful level measurements, see also Section 7 freezing point of the CO2 through as combination of heat ex-
 Marinized internals selection; for example, use of change and refrigeration. The gas is flashed into a vessel where
pressurized liquid distribution in the absorber the CO2 solidifies and separates from the gas phase. The solids
and regeneration towers, use of shorter packed are then remelted to recover the CO2 as a liquid.
beds between liquid collection/redistribution, and
higher liquid irrigation rate to ameliorate liquid Fast Cycle Pressure Swing Adsorption
maldistribution.” Some rapid cycle pressure swing adsorption installations
have been installed to remove significant levels of CO2 as well
as nitrogen and heavier hydrocarbons, so that the treated natu-
EMERGING TECHNOLOGIES ral gas can meet the required sales specifications.84
This sub-section of Section 21 is intended to mention recent- Ucarsol LE Solvents
ly developed technologies in hydrocarbon treating which have
not yet seen full scale industrial applications, but have been DOW is developing a series of hybrid solvents capable of re-
subject of past GPA and Laurance Reid Gas Conditioning con- moving mercaptans as well as acid gases.
ferences and/or publications worldwide. In future editions of
the GPSA Engineering Data Book, some of these emerging Liquid Polyols
technologies will be placed along with the industrial ones al- A new alternative for H2S and light mercaptan scavenging
ready described in the main text, while newer technologies is based on a hydroxyl stabilized polyol. Removal is quasi-in-
emerge to be mentioned first here. stantaneous and the chemical reaction is irreversible. It will
The text which follows is in the order of subject appearance also react with CO2, although much more slowly. The scavenger
in the main text, starting with chemical reaction processes and is water-based and its activity can be customized based on its
ending with batch processes. Understandably, it is beyond the concentration. Typical capacity ranges from 1.2 to 1.5 lb of H2S
scope and intent of this data book to cover every emerging tech- per gallon of product. The precise ingredients and chemical
nology worthy of mention. composition are proprietary and difficult to determine; howev-
er, it contains no nitrogen, no heavy metals and no aldehydes.
Compact Amine Processes Companies such as No Heat Resources and Exion systems have
this product available.
A compact amine process (ProCAP) has been developed by
ProPure AS. It is a continuous selective trace H2S removal pro-
cess. It relies on the rapid and selective tertiary alkanolamine
LIQUID HYDROCARBON TREATING
chemistry with H2S used in a novel co-current short residence Most raw gasoline and LPG streams contain sulfur in vari-
time contactor. The process is ideally suited for offshore applica- ous forms. LPG & raw NGL streams also can contain carbon
tions where low weight and foot print is a premium. It competes dioxide. Especially objectionable are hydrogen sulfide, mercap-
well with conventional scavenging processes as the H2S contain- tans, and elemental sulfur, which typically have maximum al-
ing solvent is regenerated and thus scavenger chemical con- lowable specifications for commercial products. Gasoline con-
sumption is avoided. taining hydrogen sulfide has an objectionable odor and may be
corrosive if water is present. Mercaptans have an objectionable
Membranes for CO2 Removal odor, and elemental sulfur can make liquid hydrocarbons cor-
from Liquid Ethane rosive. Carbonyl sulfide in LPG can hydrolyze and cause the
product to become corrosive. A product containing objectionable
It has been verified in a pilot facility utilizing a full scale materials can be treated to remove the hydrogen sulfide, car-
membrane element, that membranes can be used to remove bonyl sulfide, and elemental sulfur and to either remove the
CO2 from a liquid ethane stream. The membrane module con- mercaptans or convert them to less objectionable compounds
sists of an asymmetric hollow fiber made of cellulose-acetate. like disulfides.
Tests have shown acceptable ethane losses, while providing a
secondary benefit of removing some methane from the ethane
product.82

21-32
Mixing tional area. The tray has no outlet weir. Perry provides a calcula-
tion procedure for designing liquid-liquid contact sieve trays.73
Good mixing of hydrocarbon liquid and treating solution
may be accomplished by means of a low efficiency (40%) cen- Metal or plastic ring packing also provides good solution
trifugal pump. The gasoline stream and solution recycle stream contact in counterflow towers. One theoretical stage can gener-
join just ahead of the pump and are discharged to the solution ally be obtained in 6 to 8 feet of packed bed height. Ceramic or
settling tank. steel packing should not be preferentially wetted by the dis-
persed (hydrocarbon) phase. Previous investigations of wetting
Treaters may use static in-line mixers to obtain good gaso- properties in liquid extraction applications generally indicate
line-solution contact. A properly designed in-line static mixer that where the dispersed phase wets the packing, mass transfer
will create a controlled droplet size with a narrow size distribu- efficiency is reduced.74
tion. Continuous renewal of the dispersed phase surface area
accelerates mass transfer. The static mixer accomplishes this The packing diameter should be no larger than one-eighth of
uniform dispersion with less energy than most other devices. As the tower diameter, but normally no smaller than one-half inch.
the velocity through the static mixer increases, the pressure The hydrocarbon velocity should be about 15 GPM per square
drop increases and the mean droplet diameter decreases. A ho- foot of open tower cross sectional area.73 The hydrocarbon dis-
mogeneous mix is usually achieved in a mixer which is a few tribution nozzles should be designed with an orifice velocity in
pipe diameters in length.72 the range of one ft/sec. Higher velocities result in the formation
of small droplets which can form a hydrocarbon emulsion in the
Treated Product Clean-up treating solution leaving the bottom of the tower.74
Sand towers may be placed downstream of a liquid wash of Absorption Processes (Amines)
gasoline or LPG to remove any entrained water or solution. The
hydrocarbon flows downward through the tower. The design of Alkanolamine processes were described earlier in the gas
the tower is based on a space velocity of (4 volumes of gasoline)/ treating portion of this section. When treating hydrocarbon liq-
(volume of sand)/hour. uids with amine, contacting is generally accomplished in a liq-
uid-liquid contactor, though stirred reactors can be used. The
A water wash downstream of the treated hydrocarbon liq- tower should have a minimum of 20 feet of packing. The design
uid is also a good way to remove entrained water-based treating flow rates for packed towers should not exceed 20 gpm liquid
solutions such as caustic or amine. The process is shown in Fig. per square foot of cross sectional area.
21-28. A water circulation rate of 10 to 30 percent of the hydro-
carbon rate should be adequate, if good liquid-liquid contact is Minimizing losses of amine to liquid hydrocarbon streams
obtained. The solution concentration in the wash water should exiting the top of liquid treaters is a concern for operations.
not build up to more than 3 weight percent. Small amounts of amine in the treated liquid hydrocarbon can
result in a significant increase in chemical costs in the down-
Counterflow Contact Towers stream conditioning processes. Several studies have been con-
ducted about solubility as it is one of the factors involved to
In the liquid/liquid contact tower, the hydrocarbon feed is quantify amine entrainment. Other factors are disengagement
usually introduced through a distributor at the bottom of the time, emulsion formation and phase equilibrium. Water wash-
tower and becomes the dispersed phase. The treating solution is ing of treated LPG streams can cut 99% of the amine losses.
introduced counter currently at the top of the tower and be-
comes the continuous phase. The hydrocarbon phase migrates Fig. 21-28 shows a suggested installation arrangement with
upward through the packing due to the difference in densities of a pumparound set-up. Water from a circulation pump is inject-
the two liquids. The sweetened product is removed from the top ed through a quill to the treated LPG stream. A static mixer
of the tower where 8 to 10 feet of open column are provided for immediately downstream will promote intimate contact be-
disengagement of the heavy phase. tween the two phases before they enter a settling vessel. This
vessel should provide 15 to 20 minutes residence time, be
Counterflow contact towers can either be packed or trayed. equipped for interface level control and probably use a boot to
A sieve (perforated) tray with downcomers is probably the most help separation of the aqueous phase, whose flow rate is nor-
effective for use in liquid-liquid contact devices. The light liquid mally much smaller than the hydrocarbon flow.
flows through the perforations of each plate and is thereby dis-
persed into drops which rise through the continuous phase. The
continuous liquid flows horizontally across each plate and pass-
es to the plate beneath it through the downcomer. If the heavy FIG. 21-28
liquid is the dispersed phase, the same design may be used but Treated LPG Water Wash Schematic
turned upside down. Extraction rates are enhanced by the re-
peated coalescence and re-formation of droplets of the dispersed
phase.
For best tray efficiency, the dispersed phase must issue
cleanly from the perforations. This requires that the material of
the plates be preferentially wetted by the continuous phase or
Lean
that the dispersed phase issues from nozzles projecting beyond Amine Water Make-up
the plate’s surface. This may be formed by punching the holes
and leaving the burr in place, or otherwise forming the jets. The
liquid flowing at the larger volume rate should be the dispersed
Sour
phase. LP G
Purge to Flash Tank or
Perforations are usually 1/8 in. to 1/4 in. diameter with a to- Rich Amine Regeneration
tal hole area equal to 15 to 25 percent of the column cross-sec- Amine

21-33
Recommended water circulation flow is 3 gallons per barrel Highly corrosive conditions can be avoided by careful atten-
of treated LPG. The settling vessel can be equipped with inter- tion to operation conditions, specifically by minimizing the con-
nals to help coalescing small droplets, and thus reduce the re- tamination of the regenerated caustic system with sodium sul-
quired residence time and consequently the equipment volume. fide, and by operating the rectifying column at low pressure and
As the water exiting the bottom boot of the vessel is pumped temperature. The maximum desired steam temperature to the
back in a closed loop, the concentration of amine increases. The reboiler is 260 °F. Sulfide contamination is controlled by caustic
recommendation is to maintain an amine concentration in wa- washing of the LPG ahead of the mercaptan extractor and by
ter of 2.5 to 3 %w, therefore it is necessary to purge and make blowdown of the circulating solution. A maximum Na2S content
up. The make up flow should be set monitoring the amine con- of 0.2% is suggested.
centration, and the purge flow should be controlled by the in-
terface level controller of the vessel. The diameter of the extractor is based upon the hydrocarbon
throughput. A typical design uses flow rates of 10–15 GPM/sq ft
A white paper developed by members of GPA’s Technical of cross-sectional area for a column packed with 1-1/4 in.
Section A (Facilities Design), titled, “Design Considerations for Raschig rings. Other tower packing may be used, though the
Water Wash Installations,” may be obtained from GPA for a above throughput may change. The packed height is normally
more in depth description of this system and possible design about 30 feet in two or three packed sections to optimize disper-
alternatives. sion of the hydrocarbon phase. An additional 8–10 feet of col-
umn height is required for distribution and settling areas.
Adsorption Processes (Zeolites)
Merox®
Molecular sieve based sweetening systems can handle large
or small streams. This process reduces total sulfur content by A variation of the regenerated caustic process has been de-
removing hydrogen sulfide, mercaptans, and partially remov- veloped by UOP Process Division. Sour product is treated with
ing other organic sulfur compounds in a vessel filled with mo- caustic containing Merox catalyst to extract the mercaptans.
lecular sieve adsorbent. It will produce 1A copper-strip, doctor- The Merox solution is regenerated by oxidation with air. Disul-
sweet product. In addition, this process can be used to fides and excess air are removed overhead. Existing extraction
simultaneously dry the LPG in the same step with additional equipment with steam regeneration can be adapted to the
equipment, if sufficient bed capacity is included for this Merox process.
service.
The Merox solution gives a very high degree of removal of
The largest drawback (as in gas sweetening) is that it is lim- mercaptans in a liquid stream. If more complete removal is de-
ited in the amount of impurity that can be handled due to the sired, Merox also provides a fixed-bed catalytic conversion of
low capacity of the sieve to adsorb these impurities. In addition, mercaptans to disulfides. These disulfides will not be removed
this process requires secondary processing to sweeten the spent from the liquid stream, but will remain with the liquids. How-
regeneration gas, blending into fuel or other product stream ever, disulfides have low odor compared to malodorous, reactive
where sulfur level can be tolerated or a recycle upstream of an- mercaptans.
other processing unit, which will remove the sulfur compounds
present in the gas. Merichem®
Other Processes Merichem®79 offers several processes for the removal of H2S
and/or mercaptans from light hydrocarbon liquids. In all of
Regenerative Caustic these the key technology is use of a patented Fiber Film® bun-
dle to achieve intimate contact between the hydrocarbon feed
The regenerative caustic method of removing methyl and and the caustic solution. The bundle is comprised of long con-
ethyl mercaptans from LPG or butane employs countercurrent tinuous small diameter fibers placed in a pipe. The caustic solu-
contacting of the liquid with 10% sodium hydroxide solution in tion preferentially wets the fibers, creating a large interfacial
a packed column, and is suitable for large hydrocarbon flow area for contact with the hydrocarbon liquid. The fiber bundles
rates, while producing a doctor-sweet product. A typical flow can be installed easily into existing systems.
scheme is similar to the scheme for gas treating as illustrated
in Fig. 21-20. The caustic is regenerated in a stripping column Non-Regenerable Caustic
by the addition of free steam, or by steam internally generated
by a column heating element. A condenser may be used to con- Caustic wash can also be used to remove hydrogen sulfide,
dense water vapors that go overhead with the liberated mercap- carbon dioxide and light mercaptans from LPG and gasoline
tan vapors. The condensate is returned to the stripping column without re-generating the caustic for re-use. Liquid hydrocar-
to maintain caustic concentration. An LPG stream containing bon and recirculated caustic (Ratio 2:1) are mixed by means of
300 ppmw mercaptan sulfur can be treated doctor sweet with a pump or static mixer and discharged to a settling tank where
volume ratios of hydrocarbon to caustic as high as 33 to 1. Ap- the liquids separate. The size of the tank required is based on
proximately six pounds of steam per gallon of caustic are re- the retention time necessary for complete separation of the gas-
quired for regeneration at this hydrocarbon/caustic volume ra- oline/caustic emulsion. The retention time varies from 1-1/2
tio. The following ratios may be used to determine optimum hours for heavy gasolines to 30 minutes or less for propane. A
plant design: coalescing element on the settling tank inlet can reduce the re-
quired retention time. Since the separating tank is one-third
full of caustic, the liquid hydrocarbon retention time is based on
lb steam gal. two-thirds of the tank volume. A typical caustic wash system
4 5 6 7 8 10 12 14.5 17
NaOH utilizing a static mixer is given in Fig. 21-29.
gal. hydrocarbon
15 25 33 39 43 50 55 60 62
gal. NaOH

21-34
FIG. 21-29
Non-Regenerative Caustic

Materials of construction for caustic must consider person- For caustic treaters, the packing material is usually carbon
nel safety for every application Caustic solutions, especially raschig rings, which offer better resistance to attack by the
when hot, are extremely damaging to the human body. The ma- caustic solution.
terials selection decision must take into account potential per-
sonnel exposure and may dictate a more costly but more reliable H2S and CO2 form non-regenerable salts with caustic. Thus,
material. caustic wash is generally only applied when the quantity of
these acidic components to be removed is small.
Mild steel remains the most utilized material. It is effective in
caustic solutions up to 50 percent concentration and at tempera- Sulfur Removal
tures up to 150 °F. Corrosion rates in the range of 15–25 MPY
Elemental sulfur is removed from natural gasoline by con-
(depending on agitation, etc.) can be expected. Austenitic Ni-Cr
tacting it with a polysulfide wash solution. The solution is made
stainless steels, primarily type 304 and 316, are very resistant to
up by using the following amounts of chemicals per 1,000 gal-
caustic in concentrations up to 50 percent and temperatures to
lons of water: 1,000 lb. of caustic (NaOH), 800 lb. of commercial
about 200 °F.
Na2S, and 20 lb. of sulfur. The sodium sulfide (Na2S) is melted
Stress corrosion cracking (caustic embrittlement) has been in a vat by use of a steam lance. Add the sulfur to the melted
reported in laboratory testing79 at concentrations as low as 10 Na2S. The sulfur must be completely dissolved in the liquid sul-
percent with temperatures of 210 °F. Stress relieving of carbon fide, and then this mixture is added to the 10% (1,000 gal. water
steel is recommended for most applications. and 1,000 lb. NaOH) caustic solution. Protective clothing and
goggles should be worn when handling these chemicals.
Centrifugal pumps used in caustic circulation may experi-
ence premature seal failure which results from crystallization Carbonyl Sulfide Removal
of sodium hydroxide on the seal face. Using an API Plan 62
(external fluid quench) system with a fresh water seal flush Carbonyl sulfide (COS) can hydrolyze (react with water)
fluid or a Plan 52 (tandem seal) system with a buffer fluid are and cause sweet LPG to become corrosive. Because of this, and
good solutions. Glandless pumps (such as magnetic drive and the concern for minimizing total sulfur emissions, there has
canned motor) are also used in this application. been increased interest in removing COS from propane and
LPG streams. Several alternative processes can be used. COS
A method for calculating the acid (H2S and RSH) removal can be removed sacrificially by MEA. Mick75 has reported suc-
efficiency in a batch caustic wash system was published by Bey- cessful use of a combination of potassium hydroxide and metha-
chok in 1973,81 but is no longer included in this section. It is nol; however, this process is sacrificial. The Malaprop 76,77 pro-
shown in detail in the 11th edition GPSA Engineering Data- cess uses DGA® and requires little or no modifications in the
book as Example 21-3. process flow from that used for gas treating. The ADIP78 process
utilizes aqueous DIPA. Molecular sieves and other solid adsor-

21-35
bents can also be used for removing COS . The Malaprop, ADIP REFERENCES
and molecular sieve processes are all regenerative.
1. MSDS Number 100.240-4, March 1986.
Perco Solid Copper Chloride Sweetening 2. National Safety Council Data Sheet 1-682-80.
The PERCO® copper chloride sweetening process can be 3. Kathib, Z., “Reduction of Entrainment of Aerosols,” presented at the
used to sweeten a wide range of NGL, straight run gasoline Laurance Reid Gas Conditioning Conference, University of Oklaho-
streams and to a lesser extent kerosene to produce a doctor- ma, March 1997.
sweet product. It is a continuous process in which the mercap-
tan sulfur in the gasoline is converted to disulfides over a cop- 4. Herrin, J.P., “ Removing Very Fine Iron Sulfide Particles from Nat-
ural Gas,” presented at the Laurance Reid Gas Conditioning Confer-
per catalyst. The PERCO® process and catalyst was originally ence, University of Oklahoma, March 1994.
developed by Phillips Petroleum Co. and is now offered and sup-
ported by Chemical Products Industries, Inc. 5. Stiltner, J., “Mercury Removal from Natural Gas and Liquid
Streams,” proceedings of the 81st GPA Annual Convention, Dallas,
®
The PERCO catalyst is offered as a stationary bed of 6x30 Texas, March 2002.
mesh granular material. As manufactured, this material con-
tains approximately 10–25% water content. The catalyst loses 6. Cameron, C.J., Barthel, Y., and Sarrazin, P., “Mercury Removal
from Wet Natural Gas,” proceedings of the 73rd GPA Annual Con-
its reactivity below 7% water content and above 30% the copper
vention, New Orleans, March 1994, p. 256.
chloride can be extracted from the granular support. Adjust-
ment and/or addition of water content into the feed is generally 7. Kensell, W.W., “How to Pick a Treating Plant,” Hydrocarbon Pro-
not required. The PERCO® process can be run over a broad tem- cessing, August 1979, p. 143.
perature range, ambient to 150 ºF, optimally 120 ºF to 130 ºF. 8. Goar, B.G., and Arrington, T.O., “Guidelines Set for Handling Sour
This is convenient for two reasons: Gas,” Oil and Gas Journal, June 26, 1978, p. 160.
 It is about the same temperature as typical C 4 splitter 9. Bottoms, R.R., U.S. Patent 1,783,901 (1930).
bottoms.
10. Kohl, A.L., and Reisenfeld, F.C., Gas Purification, McGraw-Hill
 It is sufficiently high enough to prevent free water from Book Co., Inc. (1960) (Chemical Engineering Series).
condensing in the reactor.
11. Maddox, R.N, Gas and Liquid Sweetening, Campbell Petroleum Se-
Any hydrogen sulfide in the gasoline must be removed by a ries, April 1977, p. 99.
scavenger, caustic wash or other means before contact with the 12. Lee, J.I., Otto, F.D., and Mather, A.E., “The Solubility of Mixtures of
PERCO® bed. CO2 and H2S in DEA Solutions,” Canadian J. Chem. Eng., 52, p. 125
(1974).
In the sweetening reaction mercaptans are oxidized to the
disulfide and copper is reduced from cupric to cuprous. The cu- 13. Ballard, D., “How to Operate an Amine Plant,” Hydrocarbon Proc-
prous salt is simultaneously oxidized to a cupric salt by adding essing and Petroleum Refining, Vol. 45, No. 4, April 1966, p. 137.
air to the inlet gasoline stream. 14. Blake, R.J., and Rothert, K.C, “Reclaiming Monoethanolamine Solu-
The recommended charge rate is based on 1.5 volumes of tions,” Proceedings Gas Conditioning Conference 1962, University
of Oklahoma Extension Division.
gasoline/packed volume of catalyst. Air is added to the sour
charge by means of a diffusing disc at the rate of 1 cu ft of air 15. Harbison, J.L., and Dingman, J.C., “Mercaptan Removal Experi-
(STP)/bbl of charge for each 0.01% mercaptan sulfur. If the mer- ences in DGA Sweetening of Low Pressure Gas, Proceedings,” Gas
captan content of the gasoline is high, the operating pressure Conditioning Conference 1972, University of Oklahoma Extension
must be increased to hold the additional air in solution. The Division.
rate of air injection should be maintained as near to this figure 16. Holder, H.L., “Diglycolamine — A Promising New Acid-Gas Remov-
as practical since insufficient air will prevent complete oxida- er,” Oil and Gas Journal, 64, No. 18, p. 83 (1966).
tion of the cuprous salt to the cupric salt. This will create a situ-
ation where the copper in the catalyst is extracted into the hy- 17. Say, G.R., Heinzelman, F.J., Savage, D.W., et. al., “A New Hindered
Amine Concept for Simultaneous Removal of CO 2 and H2S From
drocarbon phase since the cuprous salt is soluble in this
Gases,” Chemical Eng. Progress, October 1984, p. 72.
media.
18. Goldstein, A.M., Edelman, A.M., Beisner, W.D., and Ruziska, P.A.,
Also, excess air may result in airbinding of the treater ves- “Hindered Amines Yield Improved Gas Treating,” Oil & Gas Jour-
sel and create an extremely hazardous condition. Also need to nal, July 16, 1984, p. 70.
minimize excess regeneration oxygen, which may cause corro-
sion downstream of bed. Gasoline with components that may 19. Perry, D., Fedich, R., and Parks, L., “Flexsorb ®SE A Proven Reliable
Acid Gas Enrichment Solvent,” proceedings of the 89th Annual GPA
be affected by oxygen, such as olefins, should not be treated Convention, March, 2010.
with this process.
20. Weiland, R.H., “Acid Gas Enrichment Maximizing Selectivity,”
Solid Potassium Hydroxide Laurance Reid Gas Conditioning Conference, Norman, Oklahoma,
February 2008.
Hydrogen sulfide and carbon dioxide can be removed from
LPG and gasoline by solid potassium hydroxide (KOH). KOH 21. Jones, V.W., and Pearce, R.L., “Fundamentals of Gas Treating,”
also dessicates and removes other sulfurcompounds from the liq- Laurence Reid Gas Conditioning Conference, Norman, Oklahoma,
uid. It is suggested that the bed be blown down periodically as March 1980.
a brine film can inhibit contact between the hydrocarbon and 22. Calculations conducted by the Section 21 Sub-committee using TS-
solid.88 This technology is generally applied to trace amounts of WEET software in June 2001.
H2S and CO2, as costs for frequent changeout may be
prohibitive. 23. Jones, J.H., Froning, J.R., and Claytor, E.E., Jr., Chemical Engi-
neering Data, 4, (January 1959), p. 85.

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24. Lee, J.I., Otto, F.D., and Mather, A.E., Gas Processing/Canada, 46. The Dow Chemical Company (Midland, Michigan), Dow Gas Condi-
March-April 1973, p. 26. tioning Fact Book, 1957, 1962, p. 339.
25. Dingman, J.C., Jackson, J.L., Moore, T.F., and Branson, J.A., “Equi- 47. Guillory, G., and Leppin, D., “GRI Scavenger CalcBase(TM) Soft-
librium Data for the H2S-CO2 Diglycolamine Agent-Water System,” ware Comprehensive Scavenging Resource,” Laurance Reid Gas
62nd Gas Processors Association Annual Meeting, San Francisco, Conditioning Conference, Norman OK, February 1996.
March 14-16, 1983.
48. Leppin, D., et al., Modeling Direct Injection of H 2S Scavenger in
26. Jou, F.-Y., Otto, FD., and Mather, A.E., “Solubility of H 2S and CO2 Pipelines: Laboratory Investigations and Improved Computer Mod-
in MDEA Solutions,” 1981 AIChE annual meeting. el, GPA Annual Convention, 2009.
27. Jou, F.-Y, Otto, FD., and Mather, A.E., “Solubility of mixtures of 49. Perry, C.R., “A New Look at Iron Sponge Treatment of Sour Gas,”
H2S and CO2 in MDEA Solutions,” 1986 AIChE annual meeting. Proceedings of Gas Conditioning Conference 1970, University of
Oklahoma Extension Division.
28. Kent, R.L., and Eisenberg, Hydrocarbon Processing, February 1976,
p. 87. 50. Bhatia, K., and Edwards, M. “Application of Sulfa-Check in the Gas
Industry,” proceedings of the GRI Liquid Redox Sulfur Recovery
29. Williams, W.W., “How to Remove Mercaptans from Natural Gas,”
Conference Austin Texas, April 1992 p. 353.
Hydrocarbon Processing and Petroleum Refiner, Vol. 43, No. 7, July
1969, p. 121. 51. Woodward, C., “Temporary Sweetening Unit Aids Early Oil, Gas
Production,” Oil & Gas Journal, February 13, 1995, p. 74.
30. Picciotti, M., “Optimize Caustic Scrubbing Systems,” Hydrocarbon
Processing, May 1978, p. 201. 52. Woodward, C., paper at GASTECH 96, Vienna, December 1996.
31. Tennyson, R.N., and Schaaf, R.P., “Guidelines Can Help Choose 53. Turnock, P.H., and Gustafson, K.J., “Advances in Molecular Sieve
Proper Process for Gas Treating Plants,” Oil and Gas Journal, Janu- Technology for Natural Gas Sweetening,” Proceedings Gas Condi-
ary 10, 1977, p. 78. tioning Conference 1972, University of Oklahoma Extension
Division.
32. Kutsher, G.S., Smith G.A., and Greene, P.A., “Sour Gas Scrubbing-
Allied Chemical Solvent Process,” Proceedings of the 46th NGPA 54. Leppin, D., and Dalrymple, D.A., “Overview of Liquid Redox Tech-
Annual Convention, March 14-16, 1967, Houston, TX. nology for Recovering Sulfur from Natural Gas,” Laurance Reid Gas
Conditioning Conference, Norman, Oklahoma, March 2000.
33. Hegwer, A.M., and Harris, R.A., “Selexol Solves High H 2S/CO2Prob-
lem,” Hydrocarbon Processing, Vol. 49, No. 4, April 1970, p. 103. 55. Hileman, O.E., “Liquid Redox Desulfurization,” 1991 GRI Liquid
Redox Conference.
34. Kohl, A.L., and Miller, F.E., U.S. Patent 2,926,751, March 1, 1960.
56. DeBerry, D.W., “Chemical Issues and Evolution of Liquid Redox
35. Mak, John, et al., “Advances in Fluor Solvent Technology,” Proceed-
Sulfur Recovery Processes,” proceedings of the 7th GRI Sulfur Re-
ings of the 89th Annual GPA Convention, 2010, Austin, TX. covery Conference, Austin, Texas, Sept 1995, p. 453.
36. Laborie, G., Cadours, R., Barreau, A., and Lecomte, F., “IFPEXOL: 57. Hardison, L.C., “Catalytic Gas Sweetening Process Selectively Con-
An Attractive Solution for RSH and COS Removal From Natural verts H2S to Sulfur, Treats Acid Gas,” Oil and Gas Journal, p. 60,
Gas,” Laurance Reid Gas Conditioning Conference, Norman, Okla- June 4, 1984.
homa, February 2001.
58. Hardison, L.C., “Treating Hydrogen Sulfide: An Alternative to
37. Wendt, C.J., “The Purisol Process for Acid Gas Treatment,” Proceed-
Claus,” Chemical Engineering, p. 62, January 21, 1985.
ings Gas Conditioning Conference 1969, University of Oklahoma
Extension Division. 59. Hardison, L.C., “Go From H2S to S in One Unit,” Hydrocarbon Pro-
cessing, p. 70, April, 1985.
38. Menzel, J., et al., “Gas Treating Advances With New Physical Sol-
vent Process — First Commercial Plant Operating Experience At 60. Ballaguet, J.P., et al., “Direct H 2S Removal from High Pressure
DEGT’s Kwoen Plant,” 83rd Annual GPA Convention, New Orleans Natural Gas with the Sulfint HP Redox Process,” presented at Sul-
LA, March 2004. fur 99, Calgary, Alberta, Canada.
39. Newman, S.A., Editor, Acid and Sour Gas Treating Processes, Gulf 61. Ballaguet, J.P., and Streicher, C., “Pilot Operating Experience with
Publishing Company, 1985, pp. 112-130. a New Redox Process for the Direct High Pressure Removal of H2S,”
80th GPA Annual Convention, San Antonio, Texas, March 2001.
40. Nasir, P., “A Mixed Solvent to Achieve Low Sulfur Content,” pre-
sented at the AICHE National Meeting, San Diego, California, 62. Seeger, D.M., Dalrymple, D.A., and Petrinec, B.J. “CrystaSulf —
1990. One-step H2S to Sulfur Conversion for High Pressure Natural Gas,”
Proceedings of the 84th Annual GPA Convention, March 2005, San
41. Zwet, G., Claessen, M., Taylor, C., Wijntje, R., Patil, P., and Schnei-
Antonio, TX.
der, A., “Sulfinol-X — Leveraging the Advantages of Well-Proven
and Established Technologies in a Single Acid Gas Removal Pro- 63. Weller, J.D., Weller, J., and Seeger, D. “Liquid Phase Claus Process
cess,” presented at the GPA Annual Convention, San Antonio, 2009. — New Generation H2S Removal Technology,” Proceedings of the
1st International Gas Technology Conference, Sept 21, 2009, Mos-
42. Benson, H.E., and Parrish, R.W., “HiPure Process Removes CO 2/
cow, Russia.
H2S,” Hydrocarbon Processing, April 1974, p.81.
64. Dortmundt, D., and Doshi, K., “Recent Developments in CO2 Remov-
43. Eickmeyer, A.G., Wiberg, E.A., and Gangriwala, H.A., “Energy Sav-
al,” The 14th Petroleum Conference, Cairo, Egypt, October, 1998
ings in the Gas Patch Using Catacarb Processes,” Petroenergy 81,
Houston, Texas, September 1, 1981. 65. Koch, D.R., Buchan, W.R., and Cnop, T., “Proper Pretreatment Sys-
tems Reduce Membrane Replacement Element Costs and Improve
44. Perry, C.R., “Activated Carbon Filtration of Amine and Glycol Solu-
Reliability,” Proceedings of the 84th Annual GPA Convention,
tions,” Proceedings Gas Conditioning Conference 1974, University
March 2005, San Antonio, TX.
of Oklahoma Extension Division
66. Lallemand, F., and Minkkinen, A., ”Highly Sour Gas Processing in
45. API RP 945, Avoiding Environmental Cracking in Amine Units, an Ever-Greener World,” Proceedings of the 80th Annual GPA Con-
para. 3.2.3. vention, March 2001, San Antonio, TX

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67. Goddin, C.S., “Comparison of Processes for Treating Gases with BIBLIOGRAPHY
High CO2 Content,” 61st Annual GPA Convention, March 1982.
Campbell, J.M., Gas Processing and Conditioning, Vol I and II, 9th Edi-
68. Clarke, M.A., et.al., “Designing an Optimized Injection Strategy for tion, Second Printing, May 2014.
Acid Gas Disposal without Dehydration” proceedings of the 78th
GPA Annual Convention, March 1999, Nashville, TN Dow Gas Conditioning Fact Book, Dow Chemical Co., 1962.
69. Lock, B.W., “Acid Gas Disposal: a Field Perspective,” proceedings of Kohl, A.L. and Nielsen R.B., Gas Purification, Gulf Publishing Co., 5th
the 76th GPA Annual Convention, March 1997, San Antonio, TX Edition 1997.
70. Carroll, J.J., and Maddocks, J.R., “Design Considerations for Acid Newman, S.A., Editor, Acid and Sour Gas Treating Processes, Gulf
Gas Injection,” Laurance Reid Gas Conditioning Conference, Nor- Publishing Co. (1985).
man, Oklahoma, March 1999.
71. Wall, Robert and Daryl Kenefake, “Acid Gas Injection Facilities for GPA RESEARCH REPORTS
Gas Disposal at the Shute Creek Treating Facility,” International
Petroleum Technology Conference, November 21–23 2005, Doha, Listed below are GPA Research Reports that deal with
Qatar. amine enthalpies, acid gas equilibrium and other topics cited in
this section.
72. Koch Engineering Company, Bulletin KSM-5, 1986.
73. Perry, R.H., and Chilton, C.H., Chemical Engineer’s Handbook, 5th Report Title
Edition, McGraw Hill Book Co., NY, 1973, p. 21-19.
RR-85 Enthalpies of Solutions of CO2 in Aqueous Diglycola-
74. Russell, R.M., “Liquid-Liquid Contactors Need Careful Attention,” mine® Solutions Scott P. Christensen, James J. Chris-
Oil & Gas Journal, December 1, 1980, p. 135 tensen and Reed M. Izatt, Brigham Young University,
75. Mick, M.B., “Treat Propane for COS Removal,” Hydrocarbon Pro- Provo, Utah. Project 821-84.
cessing, July 1976, p. 137. RR-102 Enthalpies of Solution of CO2 in Aqueous Methyldietha-
76. McClure, G.P., and Morrow, D.C., “Amine Process Removes COS nolamine Solutions Keith E. Markley, James J. Chris-
from Propane Economically,” Oil and Gas Journal, July 2, 1979, p. tensen and Reed M. Izatt, Brigham Young University,
107. Provo, Utah. Project 821.
77. Weber, S., and McClure, G., “New Amine Process for FCC Desulfur- RR-104 Equilibrium Solubility of Carbon Dioxide or Hydrogen-
izes Light Liquid Streams,” Oil and Gas Journal, June 8, 1981,p. Sulfide in Aqueous Solutions of Monoethanolamine, Di-
161. glycolamine, Diethanolamine and Methyldiethanolamine
78. Klen, J.P., “Developments in Sulfinol and ADIP Processes Increas- R.N. Maddox, A.H. Bhairi, James R. Diers and P.A.
es Uses,” Oil & Gas International, September 1970, p. 34. Thomas, Oklahoma State University, Stillwater, Okla-
homa. Project 841.
79. Process Industries Corrosion, NACE Publication, 1986, p. 298.
80. Wizig, H.W., “An Innovative Approach for Removing CO2 and Sul- RR-108 Enthalpies of Solution of CO2 in Aqueous Diethanol-
fur Compounds From a Gas Stream,” Gas Conditioning Conference, amine Solutions Rebecca Helton, James J. Christensen
Norman, OK, March 1985. and Reed M. Izatt, Brigham Young University, Provo,
Utah, Project 821-86.
81. Beychok, M.R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley, pp. 113-143 (1973). RR-114 Enthalpies of Solution of H2S in Aqueous Diethanolamine
Solutions Rebecca Van Dam, James J. Christensen, Reed
82. Lidal, H. Nilsen, J.I., Isaksen, H., and Hoang-Dinh, V., “CO2 Re-
moval at Sleipner,” Laurance Reid Gas Conditioning Conference M. Izatt, and John L. Oscarson, Brigham Young Univer-
University of Oklahoma, March 1998. sity, Provo, Utah. Project 821.

83. Gall, G.H., and Sanders, E.S., “Removal of Carbon Dioxide from RR-124 Equilibrium Solubility of CO2 or H2S in Protonated Solu-
Liquid Ethane Using Membrane Technology,” 81st GPA Annual tions of DEA at Low Partial Pressures R. N. Maddox and
Convention, Dallas, Texas, March, 2002. E. M. Elizondo, Oklahoma State University, Stillwater,
84. Nichols J.L.V., et al., “Processing Technologies for CO 2 Rich Gas,” Oklahoma. Project 841.
88th GPA Annual Convention, San Antonio, TX, March 2009. RR-125 Equilibrium Solubility of CO2 or H2S in Protonated So-
85. Toreja, J., VanNostrand, B., Chan, N., and Dickinson, J.P., “Rotary- lutions of DEA R. N. Maddox, M. Abu-Arabi and E. M.
Valve, Fast Cycle Pressure-Swing Adsorption Technology Allows Elizondo, Oklahoma State University, Stillwater, Okla-
West Coast Platform to Meet Tight Californai Specifications and homa. Project 841.
Recover Stranded Gas,” presented at 61st Laurence Reid Gas Con-
ditioning Conference, Norman, OK, February 2011. RR-127 Enthalpies of Solution of H2S in Aqueous Methyldi-
ethanolamine Solutions J. L. Oscarson, and R. M.Izatt,
87. Clarke, D.S., and Sibal, P.W., “Gas Treating Alternatives for LNG Brigham Young University, Provo, Utah. Project 821.
Plants,” 77th GPA Annual Convention, 1998.
RR 151 Reaction Kinetics of CO2 with MEA, DEA, and MDEA
88. Killgore, R.H., “Propane Sweetening with Solid Potassium Hydrox-
and in MDEA Based Blends Ralph W. Weiland, Opti-
ide”, 1965 Natural Gas Processors Association, Southern Regional
Meeting, Tyler, TX mized gas Treating Inc. Houston, Texas. Project 911.
RR 152 Physical Properties of MEA, DEA, MDEA and MDEA
Based Blends Ralph W. Weiland, Optimized gas Treat-
ing Inc. Houston, Texas. Project 911.

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RR 153 Enhanced Factors for Acid Gas Removal with Single and RR-195 Mokraoui, S., et al; GPA Research Report, RR-195; Mutu-
Mixed Amines Ralph W. Weiland, Optimized gas Treat- al Solubility of Hydrocarbons in Amine Solutions; Project
ing Inc. Houston, Texas. Project 911. 021; 2008.
RR-201 Oxygen Removal from Natural Gas Systems
RR-180 Amine BTEX Solubility Valtz, A., et al; Project 9171;
2002 RR-206 Solubility of Hydrocarbons in Amine Solutions (Draft) D.
RR-185 Solubility of Hydrocarbons in Amine Solutions Valtz, A., Mamrosh et al; Project 975-5; 2011 Planned
et al; Project 011; 2004.
TP-29 Critchfield, J., et al; Hydrocarbon / Water and Hydrocar-
bon / Aqueous Amines Mutual Solubility; 2003.

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NOTES:

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