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 introduced, all
broadly categorized as those depending on chemical reaction, possible processes are not discussed.
absorption, adsorption or permeation. Processes employing

DEFINITIONS OF WORDS AND Grain: A unit of mass where one pound is equivalent to 7,000
grains and a specification of 0.25 grain of H2S per 100 SCF is
PHRASES USED IN HYDROCARBON equivalent to an H2S concentration of 4.0 ppmv.
TREATING Mercaptan: Any of a homologous series of organosulfur com-
Absorption: A separation process involving the transfer of a sub- pounds, known as thiols that contain a sulfur-hydrogen bond
stance from a gaseous phase to a liquid phase through the (S-H). Thiols are the sulfur analogue of an alcohol of the gener-
phase boundary. al formula RSH where the “R” represents the alkyl group that
the S-H bond is attached to in lieu of a H or an O-H bond in the
Acid gases: Impurities in a gas stream usually consisting of CO2,
comparable alkane (paraffin) or alcohol. All of the materials
H2S, COS, RSH, and occasionally SO2. Most common in natu-
possess a foul odor, e.g. methyl mercaptan.
ral gas are CO2 and H2S.
Physical solvent: A liquid capable of absorbing selected gas com-
AGE: Acid Gas Enrichment
ponents by solubility alone without associated chemical
AGR/AGRU: Acid Gas Removal / Acid Gas Removal Unit reactions.
Acid gas loading: The amount of acid gas, on a molar or volumet- ppmv: A volumetric concentration of a species in a bulk fluid mea-
ric basis, that will be picked up by a solvent. sured in parts per million.
Adsorption: The process by which gaseous components adhere to Residence time: The time period for which a fluid will be con-
solids because of their molecular attraction to the solid tained within a specified volume.
surface.
Selective treating: Preferential removal of one acid gas compo-
Alkanolamine: An organic nitrogen containing compound relat- nent, leaving at least some of the other acid gas components in
ed to ammonia having at least one, if not two or three linear or the treated stream.
branched alkanol groups where only one or two could also be
Sour gas: Gas containing undesirable quantities of hydrogen sul-
substituted with a linear or branched alkyl group (e.g., as in
fide, other sulfur species (such as mercaptans or COS) and/or
methyldiethanolamine, or “MDEA”). The number of hydrogen
carbon dioxide.
atoms substituted by alkanol or alkyl groups at the amino site
determine whether the alkanolamine is primary, secondary or Sterically hindered amine: An alkanolamine containing a
tertiary. bulky substituent group close to the amino nitrogen site to
lower the stability of the carbamate ion thus inhibiting reac-
Antifoam: A substance added to the treating system to reduce
tions with CO2 directly with the amine (e.g., diisopropanol-
the tendency for the solvent to foam.
amine, or DIPA, AMP, 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 to
a plant; (2) the definition by a legal body such as the Texas
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 removes additional sulfur .
reactions.
Threshold limit value: The amount of a contaminant to which a
Doctor sweet: Describes a hydrocarbon stream which has had
person can have repeated exposure for an eight hour day with-
mercaptans removed to a level that it passes the Doctor Test
out adverse effects.
(GPA-1138).

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. The discussion in this section will deal with re-
gen sulfide. Higher concentrations and extended exposure to moval of some or all of the sulfur-containing compounds and
hydrogen sulfide will desensitize the sense of smell. The concen- carbon dioxide.
trations required for different reactions by the human body
are:1
GAS PRETREATMENT
• Threshold limit value (TLV) for prolonged exposure: 10
All gas sweetening units should have well-designed pre-
ppmv
treatment facilities. Carryover of brine or liquid hydrocarbon
• Slight symptoms after several hours exposure: 10-100 (as slugs or aerosol) from upstream production operations can
ppmv cause problems for gas treating and downstream processing
equipment. Also, field facilities are not typically designed to re-
• Maximum concentration that can be inhaled for one hour move troublesome contaminants like gas-phase heavy hy-
without serious effects such as significant eye and respi- drocarbons. These contaminants can likewise cause operational
ratory irritation: 200-300 ppmv difficulties in the sweetening process.
• Dangerous after exposure of 30 minutes to one hour: 500-
700 ppmv Inlet Separation
• Fatal in less than 30 minutes: 700-900 ppmv and above. If gross liquid carryover from an upstream facility is possi-
ble, a slug catcher is recommended. It should be sized not only
• Death in minutes: greater than 1000 ppmv for steady inlet fluid volumes, but for surge capacity to handle
slugs of liquid hydrocarbons, water, and/ or well treatment
Hydrogen sulfide is highly flammable and will combust in chemicals. See Section 17 for options regarding slug catcher
air at concentrations from 4.3 to 46.0 volume percent. Hydrogen design.
sulfide vapors are heavier than air and may migrate consider-
able distances to a source of ignition. If aerosols are a concern, an inlet filter separator is sug-
gested. Selected filter elements if combined with properly de-
Gaseous carbon dioxide is a naturally occurring gas that is signed coalescing devices can remove entrained droplets down
50% heavier than air and is colorless and odorless. It is also a to 0.3 microns in diameter. The detailed design of filter separa-
principal by-product of combustion. CO2 is inactive and there- tors is described in Section 7. Note that the effective-ness of a
fore non-flammable. CO2 will displace oxygen and can create an filter separator may be enhanced by the injection of a small
oxygen-deficient atmosphere resulting in suffocation. The prin- amount of polymer into the gas stream upstream of the filter 3.
cipal hazard of CO2 is exposure to elevated concentrations. The
atmospheric concentration immediately hazardous to life is In lieu of an inlet filter separator, a water wash column as
10% (volume).2 Because CO2 is heavier than air, its hazard po- shown in Fig. 21-1 may be placed ahead of the sweetening unit.
tential is increased, especially when entering tanks and vessels. Water washing can be particularly effective for removing glycol
“A common but erroneous belief is that CO2 simply acts as an or methanol mists or fogs as well as reducing the vapor phase
asphyxiant by lowering the oxygen level below the 16 percent concentration present. Of course, stainless steel or other corro-
minimum necessary to sustain life (at sea level). Although this sion-resistant alloys should be considered for water washing in
is frequently the case in most serious accidents, CO2 begins to a sour environment. Trays can be sieve type, valves or other de-
have a noticeable effect on normal body functions at about two sign as recommended by a vendor. Most of the time weirs are
to three percent. The concentration of carbon dioxide in the 2.5 to 3 inches high, and a reasonable pressure differential for
blood affects the rate of breathing, a measurable increase re- the gas stream is 1.5 psi. A demister pad is recommended at the
sulting from a level of one percent in the inspired air.”2 gas outlet.
Anyone engaged in the design or operation of a facility in which Water circulation rate should be 1 gallon per each 5 to 7 Mscf
H2S and/or CO2 are present should seek expert advice for detailed of gas (or 10 GPM per 80 to 100 MMscfd of gas). The recommend-
safety precautions and mechanical design considerations. ed make up rate is 2 to 3% of the circulation, but this figure can
be changed based on analytical results. The source of make up
TYPES OF CONTAMINANTS water can be stripped sour water, if available in the plant.
Ammonia (NH3) A white paper developed by members of GPA’s Technical
Hydrogen sulfide (H2S) Section A (Facilities Design), titled, “Design Considerations for
Hydrogen cyanide (HCN) Water Wash Installations”, may be obtained from GPA for a
Carbon dioxide (CO2) more in depth description of this system and possible design
Carbonyl sulfide (COS) alternatives.
Carbon disulfide (CS2)
Mercaptans (RSH) In the case of fine iron sulfide blowing in a dry pipeline, a
Nitrogen (N2) glycol wash column has been reported to be an effective means
Water (H2O) of solids removal4.
Sulfur dioxide (SO2) For liquid hydrocarbon treatment, a filter coalescer may be
Elemental sulfur used to remove suspended water or glycol prior to further
Mercury and arsenic processing.
Oxygen

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

Rich Amine

Stripped Sour Water Make-up

Sour
Gas

Purge to SWS

Hydrocarbon Dewpoint Control • Use thermal oxidation by using a catalyst to consume the
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-
ble to reduce the heavy hydrocarbon content of the incoming • Use an iron-based oxidation catalyst that is activated
gas through cooling (via Joule-Thomson expansion, propane re- with hydrogen sulfide or other organic sulfur compounds
frigeration, or turbo-expansion as described in Section 16), and to remove the free oxygen.
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-
An alternative means to remove gaseous heavy hydrocar- ence of low amounts of oxygen might be tolerated.
bons is through adsorption. Typically silica gel beds may be
• Treat the symptom.
used in parallel such that one bed is regenerated while the oth-
er is in service. The beds are regenerated by heating and de- • Corrosion inhibitors, filtration and/or alternate schemes
sorbing the hydrocarbons. The heavy hydrocarbons are recov- may be utilized to stop or offset any adverse effects of ox-
ered from the regeneration gas via condensation. ygen contamination.
Another alternative is to use a composite membrane where A GPA report (RR-201) reviewing technology for oxygen
a rubbery polymer provides the selective membrane layer. This removal from natural gas is listed at the end of this section.
technology is used in fuel gas conditioning commercially, and is
described in more detail in Section 16, Hydrocarbon Recovery. MERCURY REMOVAL
Oxygen Contamination It is not unusual for gas streams to contain 1 to 10 micro-
grams/Nm3 (approx. 0.1 to 10 ppbv) of mercury. Some gas
Oxygen entry into a hydrocarbon system is often trouble-
streams have been reported to have over 100 micrograms/m3
some. If liquid water is present, severe corrosion may occur. If
(approx. 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 cryogen-
sulfur deposition and plugging may occur. Oxygen contamina-
ic hydrocarbon recovery plants as described in Section 16. In or-
tion may be addressed by several different approaches, but the
der for the attack to occur, the mercury must be present as a
first step is to find and correct the source of oxygen entry into
free liquid. This situation cannot occur above –40°F. Technical-
the system. This is often the simplest and most cost effective
ly, mercury containing feedstocks can be handled without alu-
approach. Most oxygen leaks may be traced to compressor suc-
minum corrosion. Mercury containing equipment, which is kept
tions or pipe fittings.
at low temperature can be decontaminated by carrying out a
To eliminate oxygen contamination a number of possibilities cold, then warm purge with bone dry gas. However, this is not a
exist: practical method to be assured that mercury attack does not
occur.
• React the oxygen with chemicals.
The mercury in the feed gas can be removed with a mercury
• Chemicals such as amines, organics or inorganic com- removal bed. The bed uses a sulfur based trapping material
pounds may be added to remove free oxygen. Oxygen which reacts with the mercury to form cinnabar (HgS) on the
scavengers are available from many suppliers. bed. The trapping material is carried on activated carbon, zeo-
lite or alumina. The trapping bed is usually located downstream

21-3
of the dehydration. In this location, the gas is free of entrained Desorex®
liquids and water. Locating the bed in other locations is very
dependent on the material used as recommended by the vendor. Activated carbon provides only a limited storage capacity for
Fig. 21-2 designed to remove the mercury to 0.001 micrograms/ the strictly physical adsorption of mercury. Desorex® HGD2S
Nm.3 and HGD4S from Donau Carbon can be employed to bind mer-
cury through the process of chemical adsorption involving oxi-
Each vendor has criteria for sizing beds for their material. dation and adsorption in the form of stable compound or fixa-
Typical sizing criteria used in the industry are to design for a su- tion in metallic form as an amalgam. These Desorex® products
perficial flow velocity of about 50 ft/min and a residence time of 10 have been used to purify natural gases to levels as low as 10 ug/
seconds. With the rather small mass of mercury which is typically m3 of mercury.
removed, the beds can last many years between change outs.
HgSIV®
Calgon HGR®
UOP supplies HgSIV® adsorbents which are molecular
Solid adsorbents can remove mercury from gas to produce sieves coated with elemental silver. Mercury in the gas is
residuals in the range of 0.01–0.001 µg/Nm3. Calgon sulfur im- trapped by amalgamation with the silver. The adsorbent also
pregnated HGR® (4 x 10 mesh) and HGR®-P (4 mm dia.) car- serves the dual function of dehydrating the gas. HgSIV® is re-
bons are used for mercury removal and indicate designs remov- generated thermally, just like molecular sieves for dehydration.
ing mercury down to very low levels. Removal of both inorganic This material can be added as a layer to existing molecular
and organic mercury is achieved. By first drying the gas the de- sieve dryers5. However, one must take care to appropriately
gree of mercury removal increases. The sulfur impregnate re- handle the regeneration gas in this case, as it will contain mer-
acts with the mercury to produce a mercury sulfide that is fixed cury, which when desorbed will come off as a concentrated
in the carbon microstructure. spike.
Puraspec® CMG 271 and 273
Johnson Matthey Catalysts supplies Puraspec® fixed bed Another mercury trapping material, CMG 273 is offered by
absorbents for removal of traces, elemental and organic, of mer- Axens, which is sulfur supported on a mesoporous alumina. The
cury from hydrocarbon liquids and gases. The absorbents have advantage of this mesoporous alumina based product is its re-
been shown to be capable of providing the outlet mercury con- sistance to capillary condensation6. The larger pore size of this
centration normally specified for LNG production and are in material, compared to carbon-based trapping materials, per-
service in several European locations including an offshore oil/ mits utilization at near dew point conditions. The trapping com-
gas production platform. ponent is anchored on the alumina carrier making it completely
insoluble in liquid hydrocarbons and water. The material has
FIG. 21-2 been subjected at gas plant sites to both DEA and liquid hydro-
Mercury Removal Bed carbon carry-over with no active phase leaching. This same ma-
terial has been used to eliminate elemental mercury from LPG
and full range condensates.
CMG 271 also offered for use by Axens as a guard bed mate-
rial used for mercury removal from gas hydrocarbon streams
where the active trapping phase is a metal sulfide supported on
alumina. This material provides a high efficiency for the remov-
al of mercury from all types of gaseous flows, including natural
gas.

Organic Mercury Removal

Removal of all forms of organic mercury compounds from
natural gases and liquids requires firstly the conversion of the
compounds to elemental metallic mercury followed by trapping
materials to remove the metallic mercury formed. This requires
in the first stage some hydrogen for organo-mercury hydroge-
nolysis with a suitable catalyst. The first stage catalyst such as
MEP 841 also traps arsenic and lead impurities in the feed. The
two stage impurities removal process is called RAM and is
available from Axens.

GAS TREATING — PROCESS OPTIONS

The gas treating process can affect the design of the entire
gas processing facility including methods chosen for acid gas
disposal and sulfur recovery, dehydration, liquids recovery, liq-
uids fractionation and liquid product treating. Some of the fac-
tors to be considered in making a gas treating process selection
are:
• Air pollution regulations regarding sulfur compound dis-
posal and/or Tail Gas Clean Up (TGCU) requirements.

21-4
 • Type and concentration of impurities in the sour gas. High concentrations of hydrocarbons can cause design and
operating problems for the SRU. The effect of these components
• Specifications for the residue gas.
must be weighed when selecting the gas treating process to be
• Specifications for the acid gas. used. Further discussion of this can be found in Section 22.
• Temperature and pressure at which the sour gas is avail- Decisions in selecting a gas treating process can many times
able and at which the sweet gas must be delivered. be simplified by gas composition and operating conditions. High
partial pressures (50 psi) of acid gases enhance the possibility of
• Volume of gas to be processed.
using a physical solvent; however, the presence of significant
• Hydrocarbon composition of the gas. quantities of heavy hydrocarbons in the feed discourages using
physical solvents. Low partial pressures of acid gases and low
• Selectivity required for acid gas removal.
outlet specifications generally require the use of amines for ad-
• Capital cost and operating cost. equate treating. Process selection is not easy and a number of
variables must be weighed prior to making a process selection.
• Royalty cost for using the process.
Fig. 21-3 gives a summary for a number of processes.
• Liquid product specifications.
Controlling pH is very important in most of the processes
• Disposal of byproducts considered hazardous chemicals. discussed in this section. The following is offered to assist in
understanding electrolyte solutions and pH.
Any process which requires disposal of waste chemicals
must determine if the chemical is considered “hazardous.” The An electrolyte is a substance or material that will provide
permitting requirements and economic impact of hazardous ionic conductivity when dissolved in water. Both bases and ac-
waste disposal on a project must not be overlooked. ids, if they ionize in water, can be electrolytes. In water, acids
ionize or split, into H+ and the anion. The H+ combines with a
The importance of having an accurate analysis of the inlet water molecule to form H3O+ which is usually written as H+ and
gas stream cannot be overstressed. Process selection and eco- is referred to as a hydrogen ion, or proton. Water-soluble bases,
nomics depend on knowing all components present in the gas. on the other hand, ionize in water to produce hydroxyl or OH–
Impurities such as COS, CS2 and mercaptans (even in very ions and a cation. Pure water ionizes such that the concentra-
small concentrations) can have a significant impact on the pro- tion of H+ (and OH–) in the solution is 10–7 gram ions/liter.
cess design of both the gas treating and downstream processing
facilities.7,8 The method used for measuring hydrogen and hydroxyl ion
concentrations uses pH (from the French pouvoir hydrogene),
If the gas processing facility is to be used in conjunction with where the pH of a solution is the logarithm (base 10) of the re-
liquids recovery, the requirements for H2S, CO2, and mercaptan ciprocal of the hydrogen ion concentration (gram mole/liter).
removal may be affected. In liquid recovery plants, varying For pure water, then, the pH would be:
amounts of H2S, CO2, and other sulfur compounds will end up
in the liquid product. Failure to remove these components prior pH = log (1/ [H+]) = 7
to liquids recovery may require liquid product treating in order
to meet product specifications. In many instances, liquid treat- When a water molecule dissociates, one proton and one hy-
ing may be required anyway. droxyl ion are formed. The concentration of OH– in pure water,
then, is also 10–7 mole/liter.
When sulfur recovery is required, the composition of the
acid gas stream feeding the sulfur plant must be considered. A strong acid (or strong base) is one which ionizes complete-
With CO2 concentrations greater than 80% in the acid gas, the ly in water solution. Typical are HCl or NaOH. At an acid con-
possibility of selective treating should be considered to raise the centration of 0.1 mole/liter, the pH of a strong acid will be 1. The
H2S concentration to the sulfur recovery unit (SRU). This may following table will be helpful in understanding the relative
involve a multi-stage gas treating system in which the gas exit- concentrations of H+ and OH– in solutions of different pH.
ing the first stage is enriched by passing it through another ab-
sorption solvent loop.

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 & CO2)
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
 Concentration, mole/liter Aqueous Alkanolamine Processes
pH
H +
OH –
Originally applied to gas treating in 1930 by Bottoms9 al-
1 1.0 • 10–1 1.0 • 10–13 kanolamines have become the most widely used solvents for the
–2
removal of acid gases from natural gas streams10. Triethanol-
Acid Side (Excess 2 1.0 • 10 1.0 • 10–12 amine (TEA) was the first used commercially for gas treating. It
H+) 3 1.0 • 10–3 1.0 • 10–11 has been displaced for conventional applications by other al-
–4 kanolamines such as monoethanolamine (MEA), diethanol-
4 1.0 • 10 1.0 • 10–10
amine (DEA), diisopropanolamine (DIPA), diglycolamine®
5 1.0 • 10–5 1.0 • 10–9 (DGA®) and methyldiethanolamine (MDEA). Fig. 21-4 lists ap-
6 1.0 • 10 –6
1.0 • 10–8 proximate guidelines for a number of alkanolamine processes.
Neutral Solution 7 1.0 • 10–7 1.0 • 10–7 The alkanolamine (hereafter amine) solvent processes are
–8 –6 particularly applicable where acid gas partial pressures are low
8 1.0 • 10 1.0 • 10
and/or low levels of acid gas are desired in the residue gas. Be-
9 1.0 • 10–9 1.0 • 10–5 cause the water content of the solution minimizes heavy hydro-
10 1.0 • 10–10 1.0 • 10–4 carbon absorption, these processes are well suited for gases rich
in heavier hydrocarbons. Some amines can be used to selective-
–11
11 1.0 • 10 1.0 • 10–3 ly remove H2S in the presence of CO2.
Basic Side 12 1.0 • 10–12 1.0 • 10–2
Chemistry — The overall equilibrium reactions applicable
(excess OH-) 13 1.0 • 10 –13
1.0 • 10–1 for H2S and CO2 and primary and secondary amines are shown
below with a primary amine.11 A qualitative estimation of the
velocity of the reaction is given.
Example 21-1 — 5,000 gallons of amine solution with a pH of 12
is to be neutralized by the addition of hydrochloric acid (HCl). For hydrogen sulfide removal
How many pounds of pure HCl will be required? RNH2 + H2S ↔ RNH3+ + HS – Fast Eq 21-1
Note: This is simply an example calculation; there is no RNH2 + HS –
↔ RNH3+ + S – –
Fast Eq 21-2
practical reason for doing this in a gas treating plant.
The overall reactions between H2S and amines are simple
MW of HCL = 36.5 g/gmole since H2S reacts directly and rapidly with all amines to form
the bisulfide by Equation 21-1 and the sulfide by Equation
Solution steps 21-2.
5,000 gal. • 3.79 (liter/gal) = 1.9 • 104 liters For carbon dioxide removal
For each liter of solution the change in OH– (H+) required is 2 RNH2 + CO2 ↔ RNH3+ + RNHCOO– Fast Eq 21-3
(10-2) – (10-7) = 1.0 • 10-2 gram moles/liter
RNH2 + CO2 + H2O ↔ RNH3+ + HCO3– Slow Eq 21-4
The total requirement of HCl is
RNH2 + HCO3– ↔ RNH3+ + CO3– – Slow Eq 21-5
(1.9 • 104) liter • (1.0 • 10–2) (g mole/liter) = 190 g mole
Concerning the chemical reactions with CO2, primary
or amines (RNH2 ) such as MEA and DGA® agent, and secondary
(190 g mole)(36.5 g/gmole) amines (RR’NH) such as DEA and DIPA, differ from tertiary
= 15.3 pounds HCl amines (RR’R”N) such as TEA and MDEA.
454 (gram/pound)
Note that at a pH of 7, all of a weak acid (base) would Primary and Secondary Amines
probably not be neutralized. The pH required to have all of a
weak acid (base) neutralized will vary with the acid but will With the primary and secondary amines, the predominant
usually be less (greater) than 7. In the example all of the overall reaction (Equation 21-3) rapidly leads to the formation
HCl is neutralized because it is completely ionized in the of a stable carbamate which is slow to further hydrolyze to
water solution. bicarbonate.
The other overall reactions leading to bicarbonate (Equation
CHEMICAL SOLVENT PROCESSES 21-4) and to carbonate (Equation 21-5) are slow because they
have to proceed through the hydration of CO2.
Chemical reaction processes remove the H2S and/or CO2
from the gas stream by chemical reaction with a material in the Therefore, according to Equation 21-3 there is a theoretical
solvent solution. The reactions may be reversible or irrevers- limit to the chemical loading capacity of the primary and second-
ible. In reversible reactions the reactive material removes CO2 ary amine solutions to 0.5 mole CO2 per mole of amine, even at
and/or H2S in the contactor at high partial pressure and/or low relatively high partial pressures of CO2 in the gas to be treated.
temperature. The reaction is reversed by high temperature and/
or low pressure in the stripper. In irreversible processes the Tertiary Amines
chemical reaction is not reversed and removal of the H2S and/or Unlike primary and secondary amines, the nitrogen ( N ) in
CO2 requires continuous makeup of the reacting material. Fig. tertiary amines ( RR’R”N ) has no free hydrogen ( H ) to rapidly
21-5 shows the process flow for a typical reversible chemical form carbamate as per overall Equation 21-3. As a consequence,
solvent reaction process. Fig. 21-6 is a table of physical proper- the removal of CO2 by tertiary amines can only follow the slow
ties of pure gas treating chemicals. Figs. 21-7 through 21-9 route to bicarbonate by Equation 21-4 and carbonate by Equa-
show vapor pressures at various temperatures and freezing tion 21-5.
points and specific gravity for some of the treating chemicals.

21-6
 The slow rate of the reaction leading to bicarbonate is the rich solvent by simple flash alleviating the thermal regener-
underlying reason why tertiary amines can be considered for ation duty with consequent energy savings.
selective H2S removal. By adjusting absorption contact time,
this selectivity can be used to full advantage when near total Activated Tertiary Amines
CO2 removal is not necessary.
The use of activators mitigates the slow rate of the reaction
However the slow route to bicarbonate theoretically allows to bicarbonate for tertiary amines. Activators are generally pri-
at equilibrium a chemical loading ratio of one mole of CO2 per mary or secondary amines; they are tailored to increase both
mole of amine. Furthermore, at high partial pressure, the phys- the hydrolysis of the carbamate, and the rate of hydration of
ical solubility of CO2 in tertiary amines is far greater than in dissolved CO2, thus making the activated tertiary amines espe-
the primary and secondary amines, thus enhancing the CO2 cially suitable for efficient and economic bulk removal when se-
loading by physical solubility under these conditions. There- lectivity is not required (see discussion on MDEA).
fore, in the case of gases to be treated for bulk CO2 removal,
large amounts of CO2 can be liberated from the rich solvent us- Amine Process Flow Configuration
ing a simple flash, and thereby, reducing the thermal regenera- The general process flow for an amine treating plant is shown
tion duty with consequent energy savings. in Fig. 21-5. The basic flow configuration varies little for differ-
Therefore, in the case of sour gases to be treated for bulk ent solutions though some designs incorporate multiple feeds
CO2 removal, large amounts of CO2 can be liberated from the and contactor sections. Note that commercially-available process
simulators are available to model these solvent processes.

FIG. 21-4
Approximate Guidelines for Amine Processes1

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 0.20–0.80
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 0.35–0.44 NA 0.20–0.81
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. Might be only 60% or less of value shown for corrosive systems.
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 CO2 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
 FIG. 21-5
Typical Gas Sweetening by Chemical Reaction

Filtration

Sour natural gas enters through an inlet separator for the re- A white paper developed by members of GPA’s Technical
moval of liquids and/or solids. From the separator, the gas stream Section A (Facilities Design), titled, “Design Considerations for
is often heated about 10°F to reduce the potential for hydrocar- Water Wash Installations”, may be obtained from GPA for a
bon condensation as discussed earlier in this chapter. The gas more in depth description of this system and possible design
then enters the bottom of the contactor where it contacts the alternatives.
amine solution flowing down from the top of the column. The
acid gas components in the gas react with the amine to form a Note that the lean amine coming into the top of the contac-
regenerable salt. As the gas continues to pass up the contactor, tor must be at a sufficiently low loading and temperature such
more acid gases chemically react with the amine. The sweetened that the vapor pressure of the acid gas above the amine is low
gas leaves the top of the contactor and passes through an outlet enough to meet the treated gas specification (e.g., 4 ppm H2S,
separator to catch any solution which may be carried over. 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
The sweet gas leaving the contactor is saturated with water acid gas concentration adequately to meet the required specifi-
so dehydration, discussed in Section 20, is normally required cation. This is known as a “lean end pinch,” since there is not
prior to sale. If the amine losses are excessive, a water wash sufficient mass-transfer driving force to remove the residual
section as shown in Fig. 21-10 is typically added to the column acid gases.
to attempt to recover some of the vaporized and/or entrained
amine from the gas leaving the contactor. The water wash sec- As the solvent moves down the column and reacts with the
tion generally consists of three or four trays at the top of the H2S and CO2, the exothermic reactions increase the solvent tem-
contactor. Trays can be sieve type, valves or other design as rec- perature. Since raw gas coming coming into the bottom of the
ommended by a vendor. Weirs are 2.5 to 3 inches high. It is rec- contactor cools the solvent, there is usually a temperature “bulge”
ommended to install a demister pad on the vapor outlet. above the gas inlet. Increased temperatures tend to increase the
vapor pressure of acid gases above the enriched solvent, so it is
Amine vapors and small droplets are dissolved and coa- possible that the driving force for mass transfer is reduced to
lesced in water running in a closed loop with a circulation pump. near zero, resulting in a “rich end pinch.” In this case, additional
To control amine concentration from building up in the water, solvent will improve the situation by reducing the rich loading
some of the water is purged and made up. The purge is normal- and temperature in that portion of the column.
ly routed to the Flash Tank (Drum).
The maximum attainable pure component loading is limited
Water circulation rate should be 1 gallon per 7 Mscf of gas by the equilibrium solubility of H2S and CO2 at the absorber
(or 10 GPM per 100 MMscfd of gas). The recommended make up bottoms conditions, which may be reached in some high-load
rate is the largest of 3% of the circulation or the total system applications. Attached as Fig. 21-11 is data from GPA research
make up flow. report RR-104 on MEA, DGA® & MDEA along with the DEA

21-8
 FIG. 21-6
Physical Properties of 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

21-10
 FIG. 21-8 FIG. 21-10
Freezing Points of Aqueous Amine Solutions Typical Water Wash for Sweet Gas Leaving Amine
Contactor

Treated Gas

Water Make-up

Lean
Amine

Purge to Flash Drum

data from the 12th Edition for the equilibrium solubility of H2S
and CO2; however, it should be noted that both species are usu-
ally present, and the equilibrium limit for each species is im-
pacted by the existence of the other.
FIG. 21-11
Maximum Attainable 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
FIG. 21-9
Specific Gravity of Aqueous Amine Solutions
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

20 wt% MDEA @ 150°F

H2S partial pressure (psia) 3.24 26.3 138.1
mol H2S /mol amine 0.435 0.756 1.178
CO2 partial pressure (psia) 6.92 24.26 148.4
mol CO2/mol amine 0.4433 0.706 0.999

Regardless it is important to note most conventional

amine plants operate at significantly lower loadings than
the equilibrium limit.

Rich amine solution leaving the contactor flows through a

flash drum to flash off light hydrocarbons like methane and to
allow heavier hydrocarbons to be skimmed off as a separate liq-

21-11
uid phase. From the flash drum, the rich solution passes through 100 ppmv can be obtained at low to moderate pressures. COS
the rich/lean exchanger where heat is transferred from the hot and CS2 are removed by MEA, but the reactions are irreversible
lean solution. The heated rich amine goes to the upper portion unless a reclaimer is used. Even with a reclaimer, complete re-
of the stripper. As the solution flows down the column to the re- versal of the reactions may not be achieved. The result is solu-
boiler, it is stripped of H2S and CO2. The amine solution leaves tion loss and build-up of degradation products in the system.
the bottom of the stripper as lean solution. This lean solution is Total acid gas pick up is traditionally limited to 0.3-0.35 moles
then passed through the rich/lean exchanger and a lean cooler of acid gas/mole of MEA and solution concentration is usually
to reduce the lean solution temperature to approximately 10°F limited to 10-20 wt%. Corrosion inhibitors can be used to allow
warmer than the inlet gas temperature, to stay above the hy- much higher solution strengths and acid gas loadings. Because
drocarbon dew point. At this point, the lean solution is returned MEA has the highest vapor pressure of the amines used for gas
to the contactor to repeat the cycle. treating, solution losses through vaporization from the contac-
tor and stripper can be high. This problem can be minimized by
Acid gas stripped from the amine passes out of the top of the using a water wash.
stripper. It goes through a condenser and separator to cool the
stream and recover water. The recovered water is usually re- Diethanolamine — This process employs an aqueous solu-
turned to the stripper as reflux. The acid gas from the reflux tion of diethanolamine (DEA). DEA will not treat to pipeline
separator is either vented, incinerated, sent to sulfur recovery quality gas specifications at as low a pressure as will MEA.
facilities, or compressed for sale or reinjected into a suitable
reservoir for enhanced (see acid gas injection) oil recovery proj- Among the processes using DEA is the SNPA-DEA process
ects or for sequestration. developed by Societe Nationale des Petroles d’Aquitaine (today
Total) to treat the very sour gas which was discovered in Lacq
Reclaimer — A reclaimer is usually required for MEA and France in the 1950s. The original patents covered very high
DGA® amine-based systems. The reclaimer helps remove deg- acid gas loading of 0.9 to 1.3 moles per mole of amine. This pro-
radation products from the solution and also aids in the removal cess is used for high pressure, high acid gas content streams
of heat stable salts, suspended solids, acids and iron compounds. having a relatively high ratio of H2S /CO2. The original process
The reclaimers in MEA and DGA® systems differ. For MEA, a has been progressively improved and Total (through Prosernat)
basic solution helps reverse the reactions. Soda ash and/or uses higher DEA solution concentrations up to 40 wt% and a
caustic soda is added to the MEA reclaimer to provide a pH of high acid gas loading with corrosion control by appropriate de-
approximately 8-9; no addition is required for the DGA® re- sign and operating procedures.
claimer system. Reclaimers generally operate on a side stream
of 1-3% of the total amine circulation rate.13 Reclaimer sizing The process flow scheme for conventional DEA plants re-
depends on the total inventory of the plant and the rate of deg- sembles the MEA process. The advantages and disadvantages
radation expected. of DEA as compared to MEA are:

Reclaimer operation is a semi-continuous batch operation. • The mole/mole loadings typically used with DEA (0.35-
The reclaimer is filled with hot amine solution and, if neces- 0.82 mole/mole) are much higher than those normally
sary, soda ash is added. As the temperature in the reclaimer in- used (0.3-0.4) for MEA.
creases, the liquid will begin to distill. Overhead vapors can be • Because DEA does not form a significant amount of non-
condensed and pumped back into the amine system, but gener- regenerable degradation products, a reclaimer is not usu-
ally the reclaimer is operated at slightly above stripper column ally required. If DEA has to be reclaimed it must be done
pressure and the vapors are returned to the stripper. The initial under vacuum conditions.
vapor composition is essentially water. Continued distillation
will cause the solution to become more and more concentrated • DEA is a secondary amine and is chemically weaker than
with amine. This raises the boiling point of the solution and MEA, and less heat is required to strip the amine
amine will begin to distill overhead. Fresh feed is continually solution.
added until the boiling point of the material in the reclaimer re- • DEA forms a regenerable compound with COS and CS2
boiler reaches 280° to 300°F. At this point, distillation is contin- and can be used for the partial removal of COS and CS2
ued for a short time adding only water to help recover residual without significant solution losses.
amine in the reclaimer reboiler. The reclaimer is then cleaned,
recharged, and the cycle is repeated.14 Diglycolamine® — This process uses Diglycolamine®
brand [2-(2-aminoethoxy)] ethanol in an aqueous solution.
Reclaimer “sludge” removed during cleaning must be han- DGA® is a primary amine capable of removing not only H2S
dled with care. Disposal of the “sludge” must be in accordance and CO2, but also COS and mercaptans from gas and liquid
with the governing regulations. streams. Because of this, DGA® has been used in both natural
If needed a reclaiming company may be contracted to re- and refinery gas applications. DGA® has been used to treat
move degradation products or heat-stable salts from the amine. natural gas to 4.0 ppmv at pressures as low as 125 psig.15 DGA®
One type of reclaimer performs vacuum distillation on batches has a greater affinity for the absorption of aromatics, olefins,
of spent amine mixed with sufficient caustic to neutralize the and heavy hydrocarbons than the MEA and DEA systems.
excess acidity. Another type of reclaimer uses ion exchange res- Therefore, adequate carbon filtration should be included in the
in beds to remove heat stable salts. design of a DGA® treating unit.
The process flow for the DGA® treating process is similar to
Amines Used that of the MEA treating process. The three major differences
Monoethanolamine — Gas sweetening with monoetha- are:
nolamine (MEA) is used where there are low contactor pres-
• Higher acid gas pick-up per gallon of amine can be ob-
sures and/or stringent acid gas specifications. MEA removes
tained by using 50-60% solution strength rather than 15-
both H2S and CO2 from gas streams. H2S concentrations well
20% for MEA (more moles of amine per volume of
below 4.0 ppmv can be achieved. CO2 concentrations as low as
solution).

21-12
 • The required treating circulation rate is lower. This is a Formulated Solvents & Mixed Amines — Formulated
direct function of higher amine concentration. Solvents is the name given to a new family of amine-based sol-
vents. Their popularity is primarily due to equipment size re-
• Reduced reboiler steam consumption. duction, reduced corrosion and energy savings over most of the
Typical concentrations of DGA® range from 50% to 60% other amines.
DGA® by weight while in some cases as high as 70 wt% has All the advantages of MDEA are valid for the Formulated
been used. DGA® has an advantage for plants operating in cold Solvents, usually to a greater degree. Some formulations are
climates where freezing of the solution could occur. The freez- capable at high pressure of slipping larger portions of inlet CO2
ing point for 50% DGA® solution is –30°F. Because of the high than generic MDEA to the outlet gas and at the same time re-
amine degradation rate DGA® systems require reclaiming to moving H2S to less than 4 ppmv. Under conditions of low ab-
remove the degradation product. DGA® reacts with both CO2 sorber pressure and high CO2 /H2S ratios, such as Claus tail gas
and COS to form N, N’, bis (hydroxyethoxyethyl) urea, generlly clean-up units, certain solvent formulations can slip up to 90%
referred to as BHEEU.16 DGA® is recovered by reversing the of the incoming CO2 to the incinerator.
BHEEU reaction in the reclaimer.
At the other extreme, certain formulations remove CO2 to a
Methyldiethanolamine —Methyldiethanolamine (MDEA) level not possible with MDEA, so that the sweet gas is suitable
is a tertiary amine which can be used to selectively remove H2S for cryogenic plant feed. Formulations are also available for
to pipeline specifications at moderate to high pressure. If in- CO2 removal in ammonia plants. Finally, there are solvent for-
creased concentration of CO2 in the residue gas does cause a mulations, which remove H2S to 4 ppmv pipeline specifications,
problem with contract specifications or downstream processng, while reducing high inlet CO2 concentrations to 2% for delivery
further treatment will be required. The H2S/CO2 ratio in the to a pipeline. Typical treating applications for the gas processing
acid gas can be 10-15 times as great as the H2S/CO2 ratio in the industry, and the common treatment strategies employed using
sour gas. Some of the benefits of selective removal of H2S formulated amines, are summarized in Fig. 21-12. Several
include: general approaches are commonly used in the solvent
• Reduced solution flow rates resulting from a reduction in formulations.
the amount of acid gas removed. To achieve very low CO2 concentrations in the treated gas,
• Smaller amine regeneration unit. the formulation may contain activators, such as piperazine or
primary / secondary amines to promote CO2 removal.
• Higher H2S concentrations in the acid gas resulting in
reduced problems in sulfur recovery. In order to enhance H2S removal, and thereby allow greater
CO2 slip, stripping agents, such as inorganic acids may be
CO2 hydrolyzes much slower than H2S. This makes possible used.
significant selectivity of tertiary amines for H2S. This fact is
used by several companies who provide process designs using This need for a wide performance spectrum has led Formu-
MDEA for selective removal of H2S from gases containing both lated Solvent suppliers to develop a large stable of different
H2S and CO2. MDEA-based solvent formulations or MDEA-based solvents. In
summary, benefits claimed by suppliers are:
A feature of MDEA is that it can be partially regenerated in
For New Plants
a simple flash. As a consequence the removal of bulk H2S and
CO2 may be achieved with a modest heat input for regeneraion. • reduced corrosion
However as MDEA solutions react only slowly with CO2 (see • reduced circulation rate
chemistry) activators must be added to the MDEA soluion to
enhance CO2 absorption. If this is done, then the solvent is re- • lower energy requirements
ferred to as promoted or activated MDEA.
• smaller equipment due to reduced circulation rates For
Triethanolamine — Triethanolamine (TEA) is a tertiary Existing Plants
amine and has exhibited selectivity for H2S over CO2 at low
pressures. TEA was the first amine commercially used for gas • increase in capacity, i.e., gas through-put or higher inlet
sweetening. It was replaced by MEA and DEA because of its in- acid gas composition
ability to remove H2S and CO2 to low outlet specifications. TEA • reduced corrosion
has potential for the bulk removal of CO2 from gas streams. It
has been used in many ammonia plants for CO2 removal. • lower energy requirements and reduced circulation
rates
Diisopropanolamine — Diisopropanolamine (DIPA) is a
secondary amine which exhibits, though not as great as tertiary Formulated solvents are proprietary to the specific supplier
amines, selectivity for H2S. This selectivity is attributed to the offering the product. Companies offering these products and/or
steric hindrance of the chemical. (See later discussion on this processes include INEOS, Huntsman Corporation, Dow Chemi-
topic.) cal Company, UOP, BASF, Shell Global Solutions and Total via
Prosernat.

21-13
 FIG. 21-12 the H2S is absorbed via counter-current contacting with the de-
Common Formulated Amines Applications scending amine solvent. The AGE absorber typically operates
at low pressure (~0.5 barg, 7 psig), compatible with the operat-
Treating ing pressure of the upstream AGR regenerator overhead sys-
Gas Treating Specification/ Application
Strategy tem, but generally somewhat higher to provide the required in-
let pressure to the SRU, so that the main AGR doesn’t need to
Outlet H2S (4 PPM) & CO2 ( down to <50
Deep H2S and CO2 provide the extra pressure drop. The selective amine in the
ppmv) / Treating high pressure sour gas w/
removal AGE preferentially absorbs the H2S and allows the CO2 to re-
H2S for downstream cryogenic processing
main in the treated gas (also known as “CO2 slip”). The rich
Outlet H2S (4 ppmv) & CO2 (0.5 to 2 mol%) / amine from the bottom of the absorber is then pumped through
Deep CO2 removal
Treating high pressure sour gas w/ H2S to a rich-lean heat exchanger and on to a regenerator tower. The
w/ some CO2 slip
pipeline specifications regenerator produces an enriched acid gas product overhead
and the lean amine bottoms product to be recycled to the
Outlet CO2 down to <50 ppmv / Treating
absorber.
Deep CO2 Removal high pressure gas w/ CO2 upstream of
cryogenic processing 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
Outlet CO2 (2 mol%) / Treating high
CO2 removal with maximize the selectivity for absorbing H2S. Unfortunately, the
pressure gas w/ CO2 to pipeline
slip CO2 and H2S partial pressure driving forces in the AGE absorb-
specifications
er work against achieving these goals simultaneously.20 As the
Outlet CO2 (100-1000 ppmv) / Treating high gas moves up the absorber tower, the H2S partial pressure is
Deep CO2 removal
pressure gas to produce pipeline quality gas decreasing reducing the mass transfer driving force. At the
with bypass
(2 mol% CO2) using feed gas bypass same time, the CO2 partial pressure is increasing, making CO2
Outlet H2S (10 ppmv to 250 ppmv) w/ high
pick-up more difficult to avoid, so the concentration factor
Deep H2S removal
CO2 slip / Sulfur plant tail gas treating
achieved in each acid gas enrichment step is limited.
with high CO2 slip
applications Simplified Design Calculations — A simplified proce-
Outlet H2S (50 ppmv to 250 ppmv) w/ high dure for making rough estimates of the principal parameters
Deep H2S removal
CO2 slip / Acid gas enrichment for Claus for conventional MEA, DEA, DGA®, and MDEA amine treating
with high CO2 slip facilities when both H2S and CO2 are present in the gas is given
sulfur plant feed
below. It is based on excerpts from Jones and Pearce,21 modified
and extended by the Section 21 Subcommittee22 in 2002. The
Sterically Hindered Amines — Other amines have been procedure involves estimating the amine circulation rate and
used to treat sour gas17. One specialty amine uses steric hin- using it as the principal variable in estimating other parame-
drance (see nomenclature) to slow the rate of CO2 absorption. ters. For estimating amine circulation rate, the following equa-
This type of amine and the associated technology is different tions are suggested:
than Formulated Solvents, which create the desired formula- For MEA:
tions by blending different components with a standard amine
such as MDEA. These sterically hindered amines are very se- GPM = 41 • (Qy/x) Eq 21-6
lective for the removal of H2S in the presence of CO2. For low
0.33 mol acid gas pick-up per mole MEA assumed)
pressure applications such as AGE and TGCU, the CO2 slip can
For DEA (conventional):
be as high as 95%. An example of this technology is
FLEXSORB®SE/SE Plus solvents, marketed by ExxonMobil GPM = 45 • (Qy/x) Eq 21-7
Research and Engineering Company.18,19
(0.5 mol acid gas pick-up per mole DEA assumed)
Acid Gas Enrichment For DEA (high loading):

Normally, Acid Gas Removal units (AGRs) remove essen- GPM = 32 • (Qy/x) Eq 21-8
tially all of the H2S and CO2 from the produced natural gas. As (0.7 mol acid gas pick-up per mole DEA assumed)
discussed previously, AGRs can utilize a variety of solvents, in- For DGA®
cluding generic and formulated MDEA. In some cases, con-
trolled CO2 removal can be used using a selective solvent such GPM = 55.8 • (Qy/x) Eq 21-9
as FLEXSORB®SE or an MDEA based solvent to leave some of
the CO2 in the sales gas. However, for gas fields with high CO2 (0.39 mol acid gas pick-up per mole DGA assumed)
to H2S ratios, the acid gas stream from the AGR regenerator For activated MDEA (assuming 9:1 ratio of MDEA to DEA)
will have an unfavorably high CO2 to H2S ratio resulting in a GPM = 51.7 • (Qy/x) Eq 21-9a
poor quality feed to a Claus plant.
In the last few decades, Acid Gas Enrichment (AGE) has (0.50 mol acid gas pick-up per mole mixture assumed)
been used much more frequently to increase the H2S content in Where:
high CO2 containing acid gas streams. As the name implies,
acid gas enrichment concentrates the H2S from the AGR system Q = Sour gas to be processed, MMscfd
by further gas treatment in a second amine unit utilizing a se- y = Acid gas concentration in sour gas, mole%
lective amine solvent. Except for the use of the selective amine x = Amine concentration in liquid solution, wt% (Use
solvent, an AGE unit is similar to other traditional amine treat- Fig. 21-3 for suitable range of concentration)
ing units. Fig. 21-13 shows a simplified flow diagram of an acid
gas enrichment unit. The AGR acid gas is fed to the base of an After the amine circulation has been estimated, heat and
absorber column equipped with either trays or packing where heat exchange requirements can be estimated from the infor-

21-14
 TREATED GAS ENRICHED
OVERHEAD
CONDENSER
ACID GAS

MAKE-UP
AGE ABSORBER
WATER

LEAN REFLUX DRUM

CARBON FINES
SOLUTION
FILTER TREATER FILTER LEAN SURGE
REGENERATOR
VESSEL

10 PURGE

Standalone AGE Flow Diagram

WATER 8 REFLUX
WASH PUMP
PUMP 6

LEAN
COOLER

FIG. 21-13
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
mation in Fig. 21-14. Pump power requirements can be esti- Rich-Lean amine exchanger
mated from Fig. 21-15.
H = 45,000 • 230 = 10.4 • 106Btu/hr
Equations 21-6 to 21-9 normally provide conservative A = 11.25 • 230 = 2590 ft2
(high) estimates of required circulation rate. They should
not be used if the combined H2S plus CO2 concentration in Amine cooler
the gas is above 5 mole%. They also are limited to a maxi-
mum amine concentration of about 30% by weight. H = 15,000 • 230 = 3.45 • 106Btu/hr

The diameter of an amine plant contactor, can be estimat- A = 10.2 • 230 = 2350 ft2
ed using the following equation: Reflux condenser
Contactor diameter
H = 30,000 • 230 = 6.9 • 106Btu/hr
Dc = 44 • √Q / √P Eq 21-10
A = 5.2 • 230 = 1200 ft2
Where: Power requirements (Fig. 21-15)
Q = MMscfd gas to contactor Main amine pumps
P = Contactor pressure in psia HP = 230 • 850 • 0.00065 = 127
Dc = Contactor diameter in inches before rounding up to Amine booster pumps
nearest 6 inches.
HP = 230 • 0.06 = 14
Similarly, the diameter of the regenerator below the feed
point can be estimated using the following equation: Reflux pumps

Dr = 3.0 • √GPM Eq 21-11 HP = 230 • 0.06 = 14

Aerial cooler
Where:
HP = 230 • 0.36 = 83
GPM = Amine circulation rate in gallons per minute
Contactor diameter
Dr = Regenerator bottom diameter in inches
Dc = 44 • √30 /√865 = 44.4 inches or 48 inches rounded up.
The diameter of the section of the still above the feed point
can be estimated at 0.67 times the bottom diameter.
Regenerator diameter below feed point:
Example 21-2 — 30.0 MMscfd of gas available at 850 psig
and containing 0.6% H2S and 2.8% CO2 is to be sweetened using Dr = 3.0 • √230 = 45.5 inches or 48 inches (bottom) round-
20%, by weight, DEA solution. If a conventional DEA system is ed up to nearest 6 inches.
to be used, what amine circulation rate is required, and what Regenerator diameter above feed point:
will be the principal parameters for the DEA treating system?
Dra = 0.67 • 45.5 = 30.5 inches or 36 inches (top) round-
Solution: ed up to nearest 6 inches.

Using Equation 21-7, the required solution circulation is: EQUILIBRIUM DATA FOR AMINE-SOUR
GAS SYSTEMS
GPM = 45(Qy/x) = 45(30 • 3.4/20) = 230 gallons of 20%
One of the peculiarities of amine treating systems is the in-
DEA solution per minute. teractive effects of one acid gas constituent with amine upon
Heat exchange requirements (from Fig. 21-14) the equilibrium partial pressure of the other constituent. The
most commonly encountered sour gas constituents are H2S and
Reboiler CO2. The capacity of a given amine for either one of the acid gas
constituents alone is much greater than when the two occur
H = 72,000 • 230 = 16.6 • 106 Btu/hr
together.
A = 11.3 • 230 = 2600 ft2
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-
sented similar data for DEA solutions. Dingman et al.25 have

FIG. 21-14
Estimated Heat Exchange Requirements FIG. 21-15
Estimated Power Requirements
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
presented data for H2S and CO2 in equilibrium with commer- While the solubility limit data forms a good basis for the es-
cially used concentrations of DGA®. These data provide the ba- timation of subsaturated solubility, the calculation of the solu-
sis for predicting the equilibrium concentrations of MEA, DEA, bility at subsaturated conditions is not straightforward and is
and DGA® solutions when in contact with sour gases containing best done using a rigorous equation of state method. However,
both H2S and CO2. the solubility limit data did lend itself to simple correlation;
this correlation for a few common hydrocarbon-amine solution
Jou, Otto, and Mather investigated the solubility of H2S and systems is found in GPA Research Report RR-206. Using the
CO2 in MDEA and published data in 1981.26 Later they investi- solubility limit data, a simple method has been developed to es-
gated the solubility of mixtures of H2S and CO2 in MDEA, and timate subsaturated solubility and is described in detail in RR-
published data in 1986.27 The first paper presents solubilities 206. However, due to the non-ideality of the vapor phase in this
H2S in MDEA and solubility of CO2 in MDEA, whereas the sec- system requiring determination of fugacity coefficients (Henry’s
ond paper presents the results of varying mixtures of H2S and Law constants, when commonly defined as Hi = Pi/xi,1 are a
CO2 and their solubility in MDEA. function of temperature AND pressure for these systems) and
Kent and Eisenberg28 proposed a reaction equilibrium mod- the limited amount of VLE data, the simple method described
el to correlate/predict the vapor-liquid equilibrium between H2S in RR-206 does not provide an accurate estimation of subsatu-
and CO2 and primary or secondary ethanolamines. rated solubility across a wide range of pressures. Instead, the
data in the referenced GPA Research Reports, and solubility
They tested the model extensively against data for MEA and limit correlation in RR-206, can be used to check the results of
DEA with good results. This model allows for interpolation/ex- commercial simulation software, or as input data for commer-
trapolation of equilibrium data to compositions and tempera- cial simulation software for the creation of binary interaction
tures where no measurements have been made. parameters. Prediction of subsaturation solubility using the
GPA reports on amine enthalpies of solution and acid gas method outlined in RR-206 should only be considered when
equilibrium solubility are listed at the end of this chapter. other means of prediction are not available and when only ap-
proximate results are needed.
SOLUBILITY LIMITS OF A more complete summary and analysis of key data from
HYDROCARBONS IN AMINE these reports is contained in RR-206.
SOLUTIONS Overall Solubility Trends
In general, all gas treating solvents will dissolve hydrocar- Based on the data in the referenced GPA Research Reports,
bons in different amounts. Understanding hydrocarbon solubil- the following typical trends can be observed regarding the solu-
ity in these gas treating solvents is important for many reasons bility of hydrocarbons in amine solutions:
including, but not limited to, being able to estimate treated gas
product shrinkage (hydrocarbon loss), estimating emissions of ฀ ฀Hydrocarbon solubility in amines follows similar trends
Hazardous Air Pollutants (HAPs such as BTEX, n-Hexane, as hydrocarbon solubility in water, but the presence of
224-Trimethylpentane, among others) for health, safety and amine increases solubility significantly (also known as
permitting reasons, and estimating the level BTEX or other hy- the “salting-in” effect, with one example of a typical effect
drocarbons in the acid gas stream that might have negative im- on solubility limits shown in Fig. 21-17)
pacts to downstream processes such as sulfur removal. Exten- ฀ ฀Hydrocarbon solubility in amine solutions is strongly de-
sive experimental data has recently been gathered to quantify pendant on the specific amine used (Fig. 21-17)
hydrocarbon solubility in various gas treating amines, and the
solubility of some hydrocarbons in amine solutions is document- ฀ ฀Higher amine strength increases hydrocarbon solubility
ed in a number of GPA Research Reports (RR), including RR- (Fig. 21-17)
180, RR-185, and Technical Paper TP-29.
฀ ฀Higher temperature generally increases hydrocarbon
The term “solubility” refers to the concentration, under solubility (Fig. 21-17)
specified conditions of equilibrium, of a solute dissolved in a
solvent, generally determined from VLE measurements, and ฀ ฀Increased CO2 loading of MDEA decreases the solubility
expressed in terms of equilibrium ratio (K) values or Henry’s of aromatic hydrocarbons, with higher temperature
Law constant (H) values. With respect to the solubility of gases showing a more marked change (Fig. 21-18)
or vapors in liquids, the solubility is a function of a number of ฀ ฀Higher partial pressure of the hydrocarbon increases the
variables including pressure, temperature, and the concentra- solubility up to the point at which a separate liquid hy-
tion of the solute in the gas phase. Because it is easier to get drocarbon phase forms (referred to here as the solubility
more consistent and reliable VLLE data without disturbing limit, see Fig. 21-16)
equilibrium in the test cell for the low concentrations associated
with hydrocarbon solubility in amines, most of the data result- ฀ ฀While there is little influence on solubility limit due spe-
ing from the referenced GPA Research Reports is “solubility cifically to total system pressure (though it is measur-
limit” data. “Solubility limit” refers to the concentration of the able), solubility can be strongly dependent on total sys-
solute in the solvent where any additional increases in its gas- tem pressure (Fig 21-16)
phase partial pressure will result in the formation of a second ฀ ฀The aromatic hydrocarbons considered in the referenced
liquid phase rather than further significant increases in the sol- Research Reports tended to be more soluble in amine so-
ute concentration in the solvent for a given temperature; little lutions compared to non-aromatic compounds of the same
data below the solubility limit was gathered in the referenced carbon number, cyclic hydrocarbons tended to be more
GPA Research Reports, and only for gaining a general under- soluble than linear hydrocarbons, and olefins more solu-
standing of the relationship between solubility and solubility ble than paraffins (RR-180, RR-185, and TP-29)
limit, such that “solubility” could be estimated based on the
“solubility limit” data.

21-17
 • While solubility limits can readily be predicted by a sim- The chemical reactions involved are as follows:
ple model for some hydrocarbons and amines, estimates
of subsaturated solubility is better left to an equation of H2S + NaOH —> NaSH + H2O Eq 21-12
state model that considers the relatively large impact of
the fugacity coefficient NaSH + NaOH —> Na2S + H2O Eq 21-13

Additional details of consideration on this topic are given in H2S + 2 NaOH —> Na2S + 2H2O Eq 21-14
TP-29. This reference also provides a more complete overall
summary of the typical trends in hydrocarbon solubility in RSH + NaOH → R SNa + H2O Eq 21-15
amines and a review of the data in the literature. Further data
and literature references can also be found in RR-195. CO2 + 2 NaOH —> Na2CO3 + H2O Eq 21-16

CS2 + 2 NaOH —> 2 NaHS + CO2 Eq 21-17

CAUSTIC WASH
Caustic (NaOH) scrubbing systems can be used to treat A typical process flow diagram for a regenerative caustic
natural gas streams to remove CO2, CS2, H2S, and mer- treating process is shown in Fig. 21-19. Physical property data
captans.29 for NaOH solutions that used to be provided in the GPSA Engi-
neering Data Book have now been removed, but if required are
The process employs countercurrent contacting of the gas available in the 12th Edition.
stream with a caustic solution in a packed or trayed column
The column may contain one stage or several stages, de- Although caustic soda dissolves in water to form solutions of
pending on the required degree of removal. The multi-stage high concentration, due account must be taken of the tempera-
systems generally have different caustic concentrations ture at which these solutions separate solid hydrates. A number
ranging from 4-6 weight percent in the first stage to 8-10 of these hydrates are formed which separate from solutions at
weight percent in the latter stages. Multiple stages increase definite temperatures and concentrations from –28°C to 64.3°C
the caustic efficiency while maintaining a sufficient driving (–18.4°F to 147.7°F) and from 19% NaOH to about 74% NaOH.
force to achieve absorption.30
The spent solution is either regenerated or discarded de-
PHYSICAL SOLVENT PROCESSES
pending on what acid gas components are present in the These processes are based on physical absorption and oper-
gas stream. If only mercaptans are present, the caustic solu- ate with a flow scheme as shown in Fig. 21-20. In general, a
tion is regenerated with steam in a stripping still. If CO2 is physical solvent process should be considered when:31
present, a nonregenerable product (Na2CO3) is formed and
the solution must be discarded. As a result, the presence of • The partial pressure of the acid gas in the feed is greater
CO2 in caustic systems leads to high caustic consumption. than 50 psi.
This is a serious disadvantage of the caustic scrubbing proc- • The heavy hydrocarbon concentration in the feed gas is
ess. The spent caustic solutions are considered hazardous low.
wastes. The waste must be disposed of properly, since the
reaction can be reversed, and the H2S released if the waste • Bulk removal of the acid gas is desired.
is mixed with other higher pH aqueous streams.
• Selective removal of H2S is desired.
Natural gas is usually water washed after a caustic wash
to remove any caustic entrained in the gas prior to dehydra- These processes are economically attractive because little
tion. energy is required for regeneration. The solvents are regenerat-
ed by:
• Multi-stage flashing to low pressures.

FIG. 21-16 • Regeneration at low temperatures with an inert strip-

ping gas.
Equilibrium Ratio Values (K) for some Hydrocarbons in
Amine Solutions (from RR-180, RR-185) • Heating and stripping of solution with steam/solvent
vapors.
Amine Temperature Pressure
Hydrocarbon
Solution (F) (psia)
K In general, physical solvents are capable of removing COS,
CS2, and mercaptans. In certain instances, physical absorption
Toluene 65 w% DEA 77 75 20.2 processes are capable of simultaneously dehydrating and treat-
Toluene 65 w% DEA 140 75 64.3 ing the gas although additional equipment and higher energy
requirements may be needed to dry the solvent. The processes
Toluene 65 w% DEA 176 75 96.6 operate at ambient or subambient temperature to enhance the
solubility of the acid gases. The solvents are relatively noncor-
Toluene 50 w% MDEA 140 73 15.6
rosive so carbon steel can be used. Chemical losses are low due
Toluene 50 w% MDEA 140 1019 3.9 to low solvent vapor pressure or refrigerated conditions. Physi-
Ethyl cal solvents will absorb heavy hydrocarbons from the gas stream
50 w% MDEA 140 73 13.2 resulting in high hydrocarbon content in the acid gas stream as
Benzene
well as possibly significant hydrocarbon losses.
Cyclohexane 50 w% MDEA 140 73 316.6
Some of the physical absorption processes are summarized
Benzene* 50 w% MDEA 140 73 19.7
below.
*K value derived from hydrocarbon mixture (benzene, toluene, ethyl benzene)

21-18
 FIG. 21-17
Solubility Limit of Toluene in Amine Solutions
Liquid-Liquid Solubility Data and Model
Solubility Limit of Toluene in Amine Solution
Liquid-Liquid Solubility Data and Model
10
10
Solubility Limit of Toluene (scf Vapor/Gallon Solution)
Solubility Limit of Toluene (scf Vapor / Gallo

70
70wt%
wt%DGA
DGA
50
50wt%
wt%MDEA
MDEA
52.5
52.5wt%
wt%DGA
DGA
46
46wt%
wt%DGA
DGA
11 A
35
35wt%
wt%DGA
DGA 5500wwt% MDDEEA
t%M
GA
t%DDGA
7700wwt%
25
25wt%
wt%MDEA
MDEA
14.6
14.6wt%
wt%MEA
MEA
GA
t%DDGA
.5wwt%
5522.5
GA
t%DDGA
4466wwt%
A
MDDEEA
t%M
2255wwt%
0.1 GA
0.1 t%DDGA
3355wwt%

.6wwt%
14.6
14 MEA
t%M EA

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

Temperature
Temperature °F°F

Selexol® Rectisol Process®

This process developed by Allied Chemical Corp.32,33 uses a This process uses pure refrigerated methanol as a solvent
polyethylene glycol derivative as a solvent. The solvent is selec- and has been developed and licensed by Lurgi Oel Gas Chemie
tive for RSH, CS2, H2S, and other sulfur compounds. The pro- and Linde. The process is often applied for syngas purification
cess can be used to selectively or simultaneously remove sulfur and operates at temperatures as low as minus 30 to minus
compounds, carbon dioxide, water, as well as paraffinic, olefin- 100°F. Applications include selective or bulk removal of sour
ic, aromatic and chlorinated hydrocarbons from a gas or air components; however, the extremely low total sulfur impurities
stream. Because water and heavy hydrocarbons are highly sol- achievable with this process (< 0.1 ppmv) are not normally re-
uble in Selexol®, the treated gas from a Selexol® unit normally quired in natural gas treating applications. In the natural gas
meets both water and hydrocarbon dew point specifications. industry the process has been best suited for applications where
The vendor states that the solvent is very stable, no degrada- high concentrations of CO2 need to be removed.
tion products are formed or disposed of, and no solvent reclaim-
ing is required. Depending on the applications, the operating The process has also been used in the purification of natural
pressure could be as low as ambient though higher pressure is gas for LNG production. However, since methanol co-absorbs
preferred. Operating temperature varies from 0°F to ambient. higher hydrocarbons, implementation of the process has been
Selexol® is a UOP technology using a Union Carbide Corpora- limited to applications where only low concentrations of C2+ hy-
tion (subsidiary of The Dow Chemical Company) solvent. drocarbons are present.

Fluor Solvent Ifpex-2 Process®

This process patented by the Fluor Corporation, is based on This process developed by IFP licensed by Prosernat uses
the use of anhydrous propylene carbonate.34 The temperature refrigerated methanol solutions containing water in order to re-
of the lean solution to the absorber is usually well below ambi- duce hydrocarbon co-absorption. It is generally associated
ent, and some method of refrigerating the solvent is usually downstream of the Ifpex-1 dehydration process (see Section 20 )
necessary.35 which simultaneously extracts heavier hydrocarbons. The If-
pex-2 process attains equivalent acid gas and mercaptans re-
moval performance of the Rectisol process but at a slightly
higher solvent rate due to the lower solvent purity.36

21-19
 FIG. 21-18
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

CO2 Loading (mole/mole MDEA)

Purisol® Sulfinol® Process

This process has been developed and licensed by Lurgi Oel The Sulfinol® Process, licensed by Shell Global Solutions, is
Gas Chemie37. The solvent used is N-methyl-2-pyrrolidone used to remove H2S, CO2, COS, CS2, mercaptans and polysul-
(NMP or N-Pyrol), a high boiling point liquid. Purisol exhibits a fides from natural and synthetic gases40,41. Sulfinol® is a mix-
selectivity for H2S, like Selexol, and features equivalent process ture of Sulfolane (a physical solvent), water and either DIPA or
possibilities. MDEA (with or without Piperazine, an accelerator). Both DIPA
and MDEA are chemical solvents. It is this dual capacity as
As Purisol is also well suited for the selective removal of both a physical and a chemical solvent that gives Sulfinol® its
mercaptans; it can be used for the recovery of mercaptans from advantages.
regeneration off gases from adsorptive mercaptan removal
units. MDEA has higher capacity for CO2 absorption than DIPA.
However, the reaction kinetics with MDEA are slow. Sulfinol-
Morphysorb® X®, overcomes this drawback because of the accelerator. Since
the CO2 absorption in Sulfinol-X is higher, this reduces solvent
This physical solvent process developed by Krupp Uhde circulation by as much as 10% when compared to Sulfinol-D®.
called Morphysorb38 uses a mixture of N-formyl morpholine Because of the accelerated CO2 pickup, the absorbers are
(NFM) and N-acetylmorpholine as a physical solvent. The de- shorter with Sulfinol-X® than with aqueous MDEA.
veloper claims the process is best suited for processing gases
heavily loaded with acid components and entered commercial
service in 2002. Solvent Characteristics
Moderately fast reaction with CO2, fast reaction
HYBRID SOLVENT PROCESSES Sulfinol-D® with H2S. For complete removal of H2S, CO2 and
other sulfur compounds.
There are several gas treating processes which use the ef-
fects of both physical and chemical solvents. One of the earlier Slow reaction with CO2. For selective removal of
Sulfinol-M®
hybrid solvent processes developed by Lurgi was the Amisol H2S with partial removal of COS.
process combining amines with methanol39. Of the successfully Fast reaction with CO2 and H2S. Higher CO2
proven technologies in use today, the most widely used is absorption capacity than Sulfinol-D. For
Sulfinol-X®
Sulfinol®. complete removal of H2S, CO2 and other sulfur
compounds.

21-20
 FIG. 21-19
Regenerative Caustic

All Sulfinol® formulations can reduce the total sulfur content The overall reactions for CO2 and H2S with potassium car-
of treated gas down to low ppm levels. Sulfinol® solvents can also bonate can be represented by:
remove aromatics, thus providing potential cost savings in down-
stream processes like LNG and N2-rejection units. K2CO3 + CO2 + H2O ↔ 2 KHCO3 Eq 21-18

One disadvantage of the Sulfinol® solvents is the higher K2CO3 + H2S ↔ KHS + KHCO3 Eq 21-19
heavy hydrocarbon co-absorption. With Sulfinol-D®, a reclaimer
is sometimes required when removing CO2. Since Sulfinol-M
There are three basic process variations for the potassium
and Sulfinol-X contain MDEA in place of DIPA, a reclaimer is
carbonate process. The flow scheme required depends on the
not required as no DIPA-Oxazolidone is formed.
outlet specification of the natural gas. These are:
Selefining Process Single Stage Process
This process developed by Snamprogetti (now part of
The single stage process is shown in Fig. 21-21. Potassium
Saipem) uses tertiary amines such as dimethyl ethanol amine
carbonate is pumped to the top of a packed or trayed contactor
(DMEA) dissolved in an organic solvent with limited amounts
where it contacts the gas stream. The rich solution flows to the
of water. The process is very selective to H2S as CO2 hydration
stripper where the acid gases are stripped with steam. The lean
is almost completely avoided. It also removes other sulfur spe-
solution is then pumped back to the contactor to complete the
cies such as mercaptans, COS and CS2. It has a tendency to co-
cycle.
absorb hydrocarbons, which can to some extent be controlled by
increasing the water content of the solvent.
Split Flow Process
ALKALINE SALT PROCESS In this process scheme (Fig. 21-22) the lean solution stream
is split. Hot solution is fed to the middle of the contactor for
(HOT CARBONATE) bulk removal. The remainder is cooled to improve equilibrium
The basic process was developed by the U .S. Bureau of and is fed to the top of the contactor for trim acid gas removal.
Mines and employs an aqueous solution of potassium carbonate
(K2CO3). The contactor and stripper both operate at tempera- Two Stage Process
tures in the range of 230-240°F . The process is not suitable for In this process scheme (Fig. 21-23) the contactor is like that
gas streams containing only H2S11. If H2S is to be removed to of the split flow process. In addition, the stripper is in two sec-
pipeline specification or there are low CO2 outlet specifications, tions. A major portion of the solution is removed at the midpoint
special designs or a two-stage system may have to be used. Po- of the stripper and pumped to the lower section of the contactor.
tassium carbonate processes are somewhat effective in remov- The remainder is further stripped with steam and then cooled
ing carbonyl sulfide and carbon disulfide. prior to entering the top of the contactor.

21-21
 Numerous improvements have been made to the potassium Hi-Pure® Process
carbonate process resulting in significant reduction in capital
and operating costs. At the same time, lower acid gas concen- The Hi-Pure® process is a combination of conventional Ben-
tration in the treated gas can now be achieved. The most popu- field® potassium carbonate process and an amine process. The
lar of the carbonate processes are: gas stream is first contacted with potassium carbonate followed
by contacting with an amine. In this process it is critical to keep
Benfield® Process the downstream amine from being contaminated with the up-
stream potassium carbonate solution. The process can achieve
The Benfield® Process is licensed by UOP. Several activa- outlet CO2 concentrations as low as 30 ppmv and H2S concen-
tors are used to enhance the performance of the potassium car- trations of 1 ppmv.42
bonate solution.

FIG. 21-20
Typical Gas Sweetening by Physical Absorption

Filtration

FIG. 21-22
FIG. 21-21
Alkaline Salt: Split-Flow Process
Alkaline Salt: Single-Stage Process

~
~

21-22
Catacarb® Process ommended when foam tests on the inlet and outlet streams
show no improvement. This indicates carbon bed saturation.
®
The Catacarb Process is licensed by Eickmeyer and Associ-
ates. Activators, corrosion inhibitors, potassium salts, and wa- Filters should be located on the lean solution side in general
ter are contained in the solution. This process is mostly used in to avoid exposing personnel to hot rich solutions containing
the ammonia industry43. H2S. However, filtration on the rich side may need to be done to
remove particles that are more insoluble under the rich solution
conditions. For such a situation it is mandatory, if H2S may be
GENERAL CONSIDERATIONS FOR present (almost always at some level) that the design and oper-
SOLVENT PROCESS ating procedures reflect the need for personnel protection from
during filter maintenance.
Solution Filtration
Filtration equipment should be used continuously begin-
Filtration of the treating solution to remove entrained solids ning with the first day of plant operations. When starting up
is essential to the successful operation of a gas treating plant. the plant, the full flow filter, even if temporary, may prove its
Filtration rates should be as high as practical and may range worth by removing the scale and other solid particles and allow-
from 5 per cent of circulation to full stream. Removing particles ing much quicker and easier start-up of the plant.
down to 5 microns in size is recommended. In order to do this
efficiently, two stages of filtration may be required. The first Flash Tank (Drum)
stage, typically a cartridge-type or precoat filter, is designed to
remove particles down to the 10 micron or less range. The sec- Rich solution leaving the contactor may pass through a flash
ond stage of filtration, typically an activated carbon filter, re- tank. A flash tank is more important when treating high pres-
moves hydrocarbons and other contaminants. This is accom- sure gas. First, the drum will separate entrained gases in the
plished by adsorption. The activated carbon filter should always rich solution leaving the absorber. Second, the amount of ab-
be located downstream of the first stage filter because the depo- sorbed gas will decrease, because of the lower operating pres-
sition of solids would plug the carbon filter44. sure of the flash tank. Using a flash tank will:

The carryover of carbon fines can be controlled by either lo- • Reduce erosion in rich/lean exchangers.
cating a second cartridge-type filter immediately downstream • Minimize the hydrocarbon content in the acid 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 • Reduce the vapor load on the stripper.
fines. Large carbon granules produce fewer fines but are less ef-
ficient for adsorption. • Possibly allow the off-gas from the flash tank to be used
as fuel (may require sweetening).
Basic degradation products are identified by chromatogra-
phy and mass spectrometry. Acidic degradation products are When heavy hydrocarbons are present in the natural gas,
identified by ion chromatography exclusion. These tests are rec- the flash tank can also be used to skim off the heavy hydrocar-
ommended when the amine solution appears to lose its ability bons that were absorbed by the solution. Residence times for
to pick up acid gas. Degradation products affect the results of flash tanks in amine service are often designed with up to 10+
the conventional estimation of amine concentration by titra- minutes for the liquid phase depending on separation require-
tion. This may cause artificially high or low apparent amine ments. Inlet gas streams containing only methane and ethane
concentrations Also, the carbon bed will adsorb very little strong require shorter residence times. Rich gas streams require lon-
acid degradation products. In this case, purging or reclamation ger time for the dissociation of gas from solution and/or the sep-
of the solution is recommended. aration of liquid phases.

Carbon filters can be partially regenerated with steam or In addition, many flash drum set-ups will have a small ab-
hot steam condensate, which removes hydrocarbons and other sorption column where a sidestream of the lean solvent is used
adsorbed contaminants. Regeneration or bed change out is rec- to wash the overhead vapor to partially reabsorb any flashed
acid gas. This is often used to ensure the acid gas contact of the
vapor is suitable for use as fuel gas.
FIG. 21-23
Alkaline Salt: Two-Stage Process Vented Regenerator (Aromatics Impact)
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-
matics in the overhead need to be checked to determine whether
it can be vented without using a thermal oxidizer to incinerate
the hydrocarbons present.

Corrosion
Corrosion is an operating concern in nearly all sweetening
~
~

installations. The combination of H2S and CO2 with water prac-

tically ensures that corrosive conditions will exist in portions of
the plant. In general, gas streams with high H2S to CO2 ratios
are less corrosive than those having low H2S to CO2 ratios. H2S
concentrations in the ppmv range with CO2 concentrations of 2
percent or more tend to be particularly corrosive. Because the
corrosion in sweetening plants tends to be chemical in nature,
it is strongly a function of temperature and liquid velocity. The

21-23
type of sweetening solution being used and the concentration of • Minimize solids and degradation products in the system
that solution has a strong impact on the corrosion rate. In- through reclaimer operation and effective filtration.
creased corrosion can be expected with stronger solutions and
higher gas loadings. • Keep oxygen out of the system by providing a gas blanket
on all storage tanks and maintain a positive pressure on
Hydrogen sulfide dissociates in water to form a weak acid. the suction of all pumps.
The acid attacks iron and forms insoluble iron sulfide. The iron
sulfide will adhere to the base metal and may provide some pro- • Ensure deionized water or oxygen/chemical-free boiler
tection from further corrosion, but it can be eroded away easily, condensate is used for make up water. If available, steam
can be used to replace water loss.
exposing fresh metal for further attack.
CO2 in the presence of free water will form carbonic acid. • Limit solution strengths to minimum levels required for
The carbonic acid will attack iron to form a soluble iron bicar- treating.
bonate which, upon heating, will release CO2 and an insoluble • Pipe solution exchangers for upflow operation with the
iron carbonate, or hydrolize to iron oxide. If H2S is present, it rich solution on the tube side.
will react with the iron oxide to form iron sulfide.
• Monitor corrosion rates with coupons or suitable corro-
High liquid velocities can erode the protective iron sulfide sion probes.
film with resulting high corrosion rates. In general, design ve-
locities in rich solution piping should be 50% of those that would • Maintain adequate solution level above reboiler tube
be used in sweet service. Because of the temperature relation- bundles and fire tubes; a minimum tube submergence of
ship to corrosion, the reboiler, the rich side of the amine-amine 12 in. is recommended.
exchanger, tend to experience high corrosion rates. Because of Corrosion inhibitors used include high molecular weight
the low pH the stripper overhead condensing loop also tends to amines and heavy metal salts. The compositions are generally
experience high corrosion rates. proprietary. Certain inhibitors can only be used when only H2S
Solvent degradation products also contribute to corrosion. A or CO2 is in the gas, which allows increased solution strengths
suggested mechanism for corrosion is that degradation prod- and acid gas loadings. These inhibitors offer potential savings
ucts act as chelating agents for iron when hot. When cooled, the in both capital and operating costs for these special cases. An
iron chelates become unstable, releasing the iron to form iron example of this type of inhibitor use is in ammonia plants.
sulfide in the presence of H2S. Primary amines are thought to
be more corrosive than secondary amines because the degrada- Foaming
tion products of the primary amines act as stronger chelating A sudden increase in differential pressure across a contactor
agents. or a sudden liquid level variation at the bottom of the contactor
Several forms of stress corrosion cracking are possible in often indicates severe foaming. When foaming occurs, there is
amine sweetening systems. Amine stress corrosion cracking improper contact between the gas and the chemical solution,
can occur and is worse in hot solutions, but cracking can occur liquid hold-up increases and if uncontrolled will result in liquid
in cooler lines and both rich and lean streams. Post-weld heat carryover from the contactor. The result is reduced treating ca-
treatment (PWHT) can prevent this type of cracking45. Wet sul- pacity and sweetening efficiency, possibly to the point that out-
fide cracking and blistering can occur due to hydrogen generat- let specification cannot be met.
ed in corrosion reactions. The hydrogen can collect at small in- Some reasons for foaming are13:
clusions in the steel which delaminate and then link in a
step-wise pattern to create blisters. This is called HIC or hydro- • Suspended solids
gen induced cracking. Sometimes stress influences the cracking
• Organic acids
to cause stress oriented hydrogen induced cracking (SOHIC).
PWHT helps, but does not prevent HIC and SOHIC. HIC resis- • Corrosion inhibitors
tant steels are available. Seamless pipe is less prone to HIC
than plate steels. • Condensed hydrocarbons

Corrosion in alkaline salt processes, such as the hot carbon- • Soap-based valve greases
ate process, has been reported to range from none to severe. • Makeup water impurities
Corrosion can be expected where CO2 and steam are released
through flashing. Severe erosion can take place when carbonate • Degradation products
solution strengths exceed 40% because of the tendency to form
• Lube Oil
bicarbonate crystals when the solution cools.
• Too much anti-foam
Many corrosion problems may be solved using corrosion in-
hibitors in combination with operating practices which reduce Foaming problems can usually be traced to plant operation-
corrosion. Following are some guidelines to minimize al problems. Contaminants from upstream operations can be
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
• If available, use low temperature heat medium rather hydrocarbon dew point temperature of the outlet gas.
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-

21-24
ous types of anti-foam agents being considered for a given ap- • Adsorption processes both non-regenerable like activated
plication.46 This test should give the operator an indication of carbon and cyclically regenerated adsorbents such as mo-
which antifoam will be the most effective for the particular case. lecular sieves.
Place several drops of antifoam in 200 ml of treating solution
contained in a 1000 ml cylinder. Bubble oil-free air through the Scavenger Processes
solution at a constant rate. After five minutes have elapsed
Scavengers are chemicals which react with H2S and some-
shut off the air and start a timer. Note the height of foam at the
times other sulfur compounds like COS or mercaptans. Gener-
time the air was shut off and the amount of time required for
ally the spent product is not or cannot be regenerated so the use
the foam to break. The foam height is the difference between
of scavengers is limited to the removal of small quantities of
the height of the foam and the initial height of the liquid. The
sulfur impurities.
time for the foam to break is an indication of the stability of the
foam. A comparison of antifoams will let the operator select Scavengers can be applied in a continuous or batch mode. In
which chemical will best solve their foaming problems. Between the continuous mode the liquid scavenger is injected into the
anti-foam tests, care should be taken to clean the test cylinder gas stream after separation of liquid hydrocarbons and water.
thoroughly, because a very small amount of the prior anti-foam After introducing the scavenger via a quill or spray nozzle, or in
used may affect the test. some cases using a static mixer, and although the chemical re-
action is very fast, a sufficient length of pipe must be provided
Materials to allow mass transfer into the liquid to occur. The nature of the
Treating plants normally use carbon steel as the principal two phase flow regime, i.e., whether entrained flow (which is
material of construction. Vessels and piping should be stress preferred) or stratified flow is present is critical. The mixture is
relieved in order to minimize stress corrosion along weld seams. then separated in a coalescing filter and the resultant liquid
Corrosion allowance for equipment ranges from 1/16 in. to 1/4 product is discarded.
in., typically 1/8 in. In some instances, when corrosion is known In the batch mode the gas is passed through a vessel filled
to be a problem, or high solution loadings are required, stain- with liquid or solid scavenger agent. The batch mode has a
less steel or clad stainless steel may be used in the following higher scavenger utilization efficiency, especially if a lead lag
critical areas: configuration is used, but a much higher capital cost. In the
• Reflux condenser case of liquids overtreating the liquid scavenger can result in
sludge material forming in the tower exacerbating the difficul-
• Reboiler tube bundle ties involved during changeout.
• Rich/lean exchanger tubes Typical batch changeout periods might be on the order of ev-
ery 30 days. Too much longer than this and the size becomes
• Bubbling area of the contactor and/or stripper trays. prohibitive and too much shorter the cost of changeout opera-
• Rich solution piping from the rich/lean exchanger to the tions becomes too high. Batch tower net costs might approach
stripper. $30,000 per lb of sulfur removed.

• Bottom 5 trays of the contactor and top 5 trays of strip- The rest of this section provides information on some of the
per, if not all. more common scavenger processes employed in gas processing
services. Computer programs are available to estimate capital
Usually 304, 316, or 410 stainless steel will be used in these and operating costs of batch scavenger & liquid scavenger
areas, even through corrosion has been experienced with 410 injection applications47,48.
stainless in DEA service for CO2 removal in the absence of H2S.
L grades are recommended if the alloys are to be welded. Iron-Sponge Process — Iron sponge processes have been
used in the industry for decades. They selectively remove H2S
Controlling oxygen content to less than 0.2 ppmw is effec- from gas or liquid streams. The process is limited to treating
tive in preventing chloride SCC in waters with up to 1000 ppmw streams containing low concentrations of H2S at pressures
chloride content, at temperatures up to 570°F. There has been ranging from 25 to 1200 psig. The process employs hydrated
an increased use of duplex stainless steels, and they have been iron oxide, impregnated on wood chips.
successfully used in the water treatment industry to prevent
chloride SCC in high chloride waters. This suggests duplex Care must be taken with the iron sponge bed to maintain
stainless steels could be utilized in amine plant service where pH, gas temperature, and moisture content to prevent loss of
high chloride content is expected. As with any specialty steel, bed activity. Consequently, injections of water and sodium car-
proper fabrication techniques and welding procedures are bonate are sometimes needed. H2S reacts with iron oxide to
required. form iron sulfide and water. When the iron oxide is consumed,
the bed must be changed out or regenerated. The bed can be re-
generated with air; however, only about 60% of the previous bed
BATCH AND CYCLIC PROCESSES life can be expected.49 The bed life of the batch process is depen-
In this section, processes having chemical reactions and/or dent upon the quantity of H2S, the amount of iron oxide in the
physical adsorption are discussed. They all have the common bed, residence time, pH, moisture content, and temperature.
requirement that the process be operated as a batch or cyclic The change-out of the spent sponge beds is hazardous. Iron
system. At the end of the cycle the operator must either change sulfide is pyrophoric, and when exposed to air will rapidly oxi-
solution or regenerate in order to continue treating. dize, and can result in spontaneous combustion of the spent
Under this heading the following process classification is bed. To prevent this, the entire bed should be wetted before be-
considered: ginning the change-out operation. Regulations on sponge dis-
posal vary with location; therefore, local regulations on allow-
• Scavenger processes with liquid or solid sacrificial scav- able methods of disposal should be checked.
enging agents

21-25
 Sulfa-Check® — Sulfa-Check® is a product from Nalco, high sulfur loading capacities resulting in long bed life, is non-
which selectively removes H2S and mercaptans from natural pyrophoric and it will not agglomerate or cake in its reacted
gas in the presence of CO2. The process converts the sour gas (spent) form allowing easier change out and disposal.
directly to sulfur. This is accomplished by sparging the gas in a
buffered, water-based oxidizing solution containing sodium ni- SULFURTRAP® is applicable for H2S removal applications
trite (NaNO2). The sodium nitrite is reduced to ammonia (NH3), up to 0.5 TPD sulfur. Regardless of inlet H2S concentration,
which remains in solution. The spent product is classified as SULFURTRAP® will yield an outlet concentration of <1 ppm
non-hazardous. H2S until bed change out is required.

This process is suitable for ranges from 15 Mscf/d to 3.0 Liquid Triazine Based Scavengers — Most liquid scav-
MMscf/d and inlet H2S ranging from 10 ppmv to 3000 ppmv.50 engers are ethanol triazines, but some methanol triazines are
also in use. The active ingredient for ethanol triazine formula-
A number of variables, including some associated risks, tions is usually 1,3,5 tris (2-hydroxyethyl)-hexahydro-1,3,5 tri-
must be considered prior to determining if the Sulfa-Check® azine, but it is sold diluted to various degrees, but usually
process is applicable. For example, low levels of ammonia may around 50%, by water. The exact ingredients of the commercial
appear in the treated gas. Also, the reduction of NO2may result scavengers are often proprietary and difficult to determine,
in the formation of nitric oxide (NO). If air is present in the raw however. A typical capacity range, as directly observed in batch
gas, it will react with the nitric oxide, to form nitrogen dioxide application in the field, was 0.5 to 0.8 lb S removed per gallon of
(NO2). NO2 is a strong oxidizing agent that will react with elas- scavenger for a 50% solution of triazine in water. Ultimately,
tomers and odorants, and cause corrosion in a moist environ- what is important is not the price of the scavenger per unit vol-
ment. It is recommended that Nalco be contacted for further ume, as it is commonly sold nor the capacity per gallon, but
information. rather the amount of H2S which can be removed for a given cost
of scavenger. It may require experimentation to determine the
SulfaTreat® — SulfaTreat® is an H2S scavenging process most cost effective product.
offered by MI-Swaco. The material is a dry, free-flowing, granu-
lar substance used for selective removal of H2S from natural There are many manufacturers for these products and the
gas in the presence of CO2. The process is not affected by CO2, product names change frequently, so it is hard to provide an ac-
and it does not produce elemental sulfur or nitric oxides. Also curate list in this book. Some of the current manufacturers of
SulfaTreat® will not ignite in the vessel. Other advantages in- these products include Baker Petrolite, Clariant, Nalco, MI-
clude longer bed life and lower cost relative to the iron sponge Swaco, Swan Industries, Champion Technologies, Quaker
process. The capacity is adversely affected, if the gas is too far Chemicals, Edmunds and Assocates and BetzDearborn.
below water saturation.
Adsorption Processes
Applications for SulfaTreat® include: natural gas treating,
amine treater off gas, high concentration CO2 streams, and any Adsorption is also used to remove H2S, CO2 and other sulfur
other H2S-containing gases. contaminants from natural gases. Adsorbents used are either
regenerated such as molecular sieves or not regenerated such
MI-Swaco also offers other SulfaTreat® absorbents besides as impregnated activated carbon.
the original SulfaTreat® product for removing H2S and mercap-
tans from hydrocarbon gas & liquid streams. Molecular Sieve — Molecular sieves can be used for re-
®
moval of sulfur compounds from gas streams (Fig. 21-24). Hy-
Puraspec — Johnson Matthey Catalysts supplies the drogen sulfide can be selectively removed to meet 0.25 grain/100
Puraspec® range of processes and products for desulfurisation scf specification. The sieve bed can be designed to dehydrate
of hydrocarbon gases and liquids. The processes use fixed beds and sweeten simultaneously. In addition, molecular sieve pro-
of granular, metal oxide-based chemical absorbents, which are cesses can be used for CO2 removal.
developments of the ‘high temperature zinc oxide’ used for puri-
fication of hydrocarbon feedstocks to steam reformers in ammo- In general, the concentrations of acid gas are such that cycle
nia, hydrogen, and methanol plants. Puraspec® absorbents are times are in the order of 6-8 hours. To operate properly the
effective at temperatures down to 32°F, so no added heat is nec- sieves must be regenerated at a temperature close to 600°F for
essary, and are in service at pressures from atmospheric (treat- a long enough period of time to remove all adsorbed materials,
ing vent gases) to 1800 psia treating dense phase gas feed to a usually one hour or more. Exact arrangement of the regenera-
gas processing plant. tion cycle depends upon process conditions.
Puraspec® units are in service treating natural gas to pipe- Regeneration of a molecular sieve bed concentrates the H2S
line or petrochemical specifications.51,52 Because the absorbents into a small regeneration stream which must be treated or dis-
remove H2S and COS irreversibly, they are best suited to pol- posed of. During the regeneration cycle, the H2S will exhibit a
ishing duties. In large scale applications this can be removal of peak concentration in the regeneration gas. The peak is ap-
up to 50 ppmv or 200-400 lbs per day of sulfur. Liquid treating proximately 30 times the concentration of the H2S in the inlet
applications include removal of H2S/COS from LPG to meet cop- stream. Knowing the concentration of this stream is essential
per strip test specifications. Spent absorbents are normally sent for the design of a gas treater for the regeneration gas.
to metals refineries where they can be treated as high-grade
The problem of COS formation during processing according
ores for metals recovery.
to the reaction:
SULFURTRAP®— Chemical Products Industries, Inc pro- Eq 21-20
H S + CO ↔ COS + H O
2 2 2
vides this patented H2S absorbent/catalyst and process, which
uses a dry, free-flowing, spherical material for selective removal has been extensively studied. Molecular sieve products have
of hydrogen sulfide (H2S) and light mercaptans from natural been developed that do not catalyze COS formation53. The cen-
gas & NGLs. SULFURTRAP® is environmentally non-hazard- tral zone in the regeneration cycle is most favorable to COS
ous, is not affected by CO2, and does not need the addition of formation.
water vapor to function properly. SULFURTRAP® is capable of

21-26
 Operation of adsorbent plants is simple, but design is com- • Conversion of the formed HS− to elemental sulfur via the
plex. For example a dust filter is generally required downstream action of an auxiliary redox reagent (ARR).
of the beds to ensure that fine solid particles are not entrained
into the treated gas. Manufacturers must be consulted for po- • Separation and recovery of solid sulfur.
tential applications. Refer to Dehydration (Section 20) and the • Regeneration of the spent auxiliary reagent via reaction
gasoline and LPG treating portion of this section for additional with oxygen dissolved in the solution.
details.
The processes share the general chemistry shown below55.
Oxorbon — Oxorbon is an alternative solid bed material
which consists of activated carbon impregnated with potassium • H2S absorption using an alkaline solution:
iodide (KI). Donau Carbon markets such a carbon for the re- H2S(g) ↔ H2S(sol’n) Eq 21-21
moval of H2S and mercaptans. The adsorbed H2S is converted to
+ –
elemental sulfur by catalytic reaction under the presence of ox- H2S(sol’n) ↔ H + HS Eq 21-22
ygen. The resulting sulfur is fixed on the pores of the activated
carbon. Sulfur loadings as high as 60% of the carbon mass have Note that this is a non-selective, basic scrubbing solution;
been reported and sulfide concentrations below 1 ppmv are thus, additional acidic components (CO2 , HCN) of the sour gas
claimed. will be soluble in the scrubbing solution. While CO2 is partially
absorbed in the alkaline solution, it does not participate in the
redox reactions. CO2 may however increase the rate of con-
LIQUID REDOX PROCESSES sumption of caustic or buffering compounds. The fate of other
Processes in this group absorb H2S from gas streams and reduced sulfur species (COS, CS2, RSH, RSR) depends on the
produce elemental sulfur by reacting oxidizing/reducing agents particular process being considered.
with the H2S to form elemental sulfur and water.54 • Conversion to Elemental Sulfur:
The redox agent is then regenerated by reaction with air in HS– + H+ + 21 O2(sol’n) → H2O(1) + 81 S8 Eq 21-23
an oxidizer vessel.
Liquid redox sulfur recovery processes all share the follow- Note that, in the absence of an auxiliary redox reagent
ing major steps:55 (ARR), the reaction shown as Equation 21-23 is slow and non-
specific. The addition of an ARR increases the rate of reaction
• Sour gas cleaning by absorption of H2S into a circulating and directs the oxidation to elemental sulfur. The reaction
alkaline solution.

FIG. 21-24
Integrated Natural Gas Desulfurization

21-27
shown as Equation 21-24 is common to all the processes consid- Lo-Cat IIR
ered in this section.
The Lo-Cat II® process,57,58,59 licensed by Merichem, is an
HS– + ARR(OX) → 81 S8 + H+ + AAR(RED) Eq 21-24 improvement over the earlier Lo-Cat® process. The process can
where (OX) denotes the oxidized form and (RED) denotes the be applied directly to natural gas sweetening or treatment of
reduced form of the ARR. low-H2S acid gas for conversion of H2S to sulfur (see Section 22).
The process uses a solution of iron which is held in solution by
Regeneration of the Spent ARR Using Air: organic chelating agents. The iron in the solution oxidizes the
hydrogen sulfide to sulfur. The solution is then circulated to an
O2(g) ↔ O2(sol’n) Eq 21-25 oxidizer and regenerated for reuse in the process.
1 +
ARR(RED) + O2 (sol’n) + 2 H → ARR(OX) + H2O(1) Eq 21-26 The process will not remove CO2, COS, CS2 nor RSH. If de-
2
sired, some CO2 can be removed from the feed gas by strong
buffering of the solution. High pH has a negative impact on
The overall simplified chemistry of liquid redox processes is sulfur conversion in LoCat solution, therefore the pH needs to
thus: be maintained at the correct level. At high CO2 partial pressures
(above 30 psi), the requirement to maintain pH control can
H2S(g) + 21 O2(g) → H2O(1) + 81 S8 Eq 21-27 become a significant design issue.
Lo-Cat II utilizes special additives to reduce the rate of chel-
ant degradation. For acid gas applications, an auto-circulation
design is offered. Here, sparging of air in the oxidizer box causes
Because they share major process operations and are based
solution to flow to the next compartment, obviating the need for
on similar process chemistries, the process flow sheets and
a pump. Under proper conditions, the sulfur derived in the pro-
equipment requirements for liquid redox systems are rather
cess is suitable for sale.
similar.

Stretford Process SulFerox®

The Shell SulFerox® process, developed by Shell and the
The Stretford process was developed by British Gas PLC. It
Dow Chemical Company, is also an iron chelate redox technolo-
involves the use of vanadium salts as the ARR. The process has
gy that removes hydrogen sulfide and converts it directly to sal-
been extensively used in Europe,54 however, environmental
able sulfur in one step. The process offers low capital and oper-
concerns around the discharge of vanadium compounds has
ating costs through the use of a high concentration iron chelate
limited its use.
solution and effective control of chelate degradation. The pro-
Iron Chelate Processes cess also offers a patented contactor design to improve the over-
all efficiency of the process which further reduces capital costs.
Currently, chelates are the most commonly used auxiliary The optimum application for SulFerox® is in the one to twenty
redox reagents (ARR). A chelating agent is generally an organic tons per day range of recovered sulfur.
molecule which is able to bind with a metallic cation in such a
way that the cation is sequestered from the solution. To illus- Sulfint-HP®
trate, consider the case of iron compounds. Fe(III) is capable of
The Sulfint-HP® process is another iron-chelate based liquid
oxidizing H2S to sulfur, with subsequent formation of Fe(II).
redox technology licensed by Prosernat. It is claimed that it can
Fe(II) is easily oxidized by air back to Fe(III). However, both
be directly applied to high pressure sour gas streams. To avoid
forms of unsequestered iron will form precipitates with the sul-
the problems of sulfur plugging at elevated pressure, Sulfint-
fides or oxides in solution, thereby rendering them ineffective.
HP® applies direct filtration to the sulfur containing solution,
By chelating the iron with a compound like ethylenediaminetet-
which exits the high-pressure absorber.60 After filtration, the
raacetic acid (EDTA), the iron will not precipitate, but is still
clarified high pressure solution can then be partly recycled back
able to transfer an electron in the redox process. The process
to the absorber, thus minimizing the pumping cost, while the
solutions are monitored regularly with occasional addition of
other portion is letdown in pressure to be regenerated with air
buffering agents, and sometimes defoamers, being required.
in an oxidizer vessel. The expansion of the aqueous-based redox
A common problem with chelate-based processes is the deg- solution yields extremely low amounts of flashed gas. Sulfint-
radation of the chelating agent56. Another problem is sulfur HP® process operation has proved easy and reliable in field
plugging in the contact tower. For this reason, these processes operation.61
were usually limited to low pressures (below 300 psig), unless
combined with a high pressure amine absorber. Today direct LIQUID PHASE CLAUS REACTION
applications to high pressure sour gases have been developed
and these are mentioned hereafter.
PROCESSES
CrystaSulf, marketed by CrystaTech, Inc., is a technology
Because they share major process operations and are based
that utilizes a non-aqueous solution to absorb H2S from the pro-
on similar process chemistries, the process flow sheets and
cess stream, and react it with dissolved SO2 to form elemental
equipment requirements for liquid redox systems are rather
sulfur via the Claus reaction.62 The proprietary non-aqueous
similar. Lo-Cat, SulFerox, and Sulfint-HP are chelated iron liq-
solution does not absorb CO2, and therefore is not affected by
uid redox processes.
high partial pressures of CO2.

21-28
 After contact with the process stream, the solution is flashed Natural gas sweetening (particularly CO2) and dehydration
to lower pressure. The sour flash gas is usually vented to flare, using membranes often offer significant advantages over the
but may be compressed and returned to the inlet, if desired. The more conventional methods such as amine treating, physical
solution keeps elemental sulfur dissolved until the temperature solvents, and solid adsorbents. Membranes can be used by
is reduced in the crystallizer. There, elemental sulfur precipi- themselves or in conjunction with amine units to maximize the
tates from solution. The problem of sulfur plugging in high- benefits of both technologies. To minimize plasticization of
pressure equipment is thus avoided, and the process can be ap- membrane materials, the CO2 partial pressures are limited to
plied to high-pressure gas streams. approximately 600psi. Membranes are particularly attractive
when the pressure of the feed gas is high (over 500 psig) and/or
This alternative to liquid redox processes has recently been the CO2 content of the gas to be treated is high (over 10%). Still,
commercialized63. project specific requirements sometimes allow membranes to be
economically attractive even at CO2 levels as low as 2%, for ex-
BIOLOGICAL PROCESSES ample when the gas is already dehydrated, so that an additional
dehydration step can be avoided. Although the highest H2S par-
Among biological processes worthy to mention is the THI- tial pressures of an operating unit as of 2010 is only 20 psi,
OPAQ® process commercialized by Paques in the early 1990’s membranes could in future become attractive for bulk removal
for low pressure gas desulpherization. Subsequently, Paques of H2S in highly sour service. Bench testing indicates that at
and Shell Global Solutions developed the ShellPaques process least one of the currently available membranes has no practical
for H2S removal from higher pressure gas streams with the first maximum H2S partial pressure limit.
commercial unit starting up in 2002. The Shell-Paques process
can be considered for removing H2S in the form of bio-sulphur Other benefits of membrane systems are: a lower capital in-
for applications up to 150 long tons per day. vestment than amine plants in most cases, reduced mainte-
nance and labor costs, no moving parts, no chemical consump-
In this process a gas stream containing H2S contacts an tion, excellent flexibility in adjusting to variations in feed flow
aqueous soda solution containing sulfur bacteria in an absorb- and feed composition, and a significant space and weight ad-
er. The soda absorbs the H2S and then flows to a regenerator. vantage over amine plants. The last benefit is particularly sig-
The regenerator consists of an aerated atmospheric tank where nificant in offshore applications.
hydrogen sulfide is biologically converted to sulfur. The sulfur
may be recovered as a moist filter cake or as a liquid product. FIG. 21-25
Typical Relative Cellulose Acetate Membrane Properties
MEMBRANE SEPARATION PROCESS (Courtesy UOP, A Honeywell Company)
Membranes are thin, polymer-based barriers that allow Relative
preferential passage of certain substances over others64. Gas
separation through membranes relies on the principle that gas- H2O 100
es dissolve in and diffuse through membrane polymers. Certain He/H2 30
gases like H2O, H2S, and CO2 will permeate through a mem-
brane at a faster rate than hydrocarbons due to differences in H 2S 15
diffusivity and solubility of those gases through that membrane CO2 12
as shown in Fig. 21-25. The difference in gas permeability rates
through the membrane provides the basis for the separation. CS2 7
The separation is driven by the component partial pressure dif- COS 2
ferences across the polymer membrane.
CO 1
Therefore the technology is effective for bulk removal of
Nitrogen 1
CO2 and H2S and is less applicable for very stringent sour gas
specifications. They are very attractive for use where there is a Methane 1
final sweetening process like an amine unit or a H2S polishing
Ethane 1/3
bed available downstream. However, if the inlet sour gas has
already been dehydrated, membranes can be attractive for Propane 1/10
meeting CO2 product specifications down to 2% CO2 in some
Butane 1/15
applications.
Pentane 1/20
In the design of membrane systems for these purposes it is
important to focus on achieving high selectivity of CO2 vs. natu- Hexane 1/25
ral gas in order to avoid natural gas losses. To maximize the hy-
drocarbon recovery, recycling and reprocessing of the permeate
The table provides typical selectivity numbers to highlight
gas is often required to avoid prohibitive natural gas losses. In
where membrane separation can be used effectively. The actual
all membrane systems proper pre-conditioning of the inlet gas
membrane properties can be highly dependent on pressure,
is critical to avoid premature membrane deactivation. Selecting
temperature, flow and composition. It is recommended to check
the right membrane pretreatment is the key to maximize life-
time of the membrane material employed65. with the membrane supplier for proper evaluation.

Several large membrane systems, including some treating Highly Sour Gas Pretreatment Processes
over 500 MMscfd of gas containing over 30 mol% CO2 have been
successfully implemented as a result of advances in pretreat- If the acid gas content is over 15% then another class of pro-
ment technology. cesses, in addition to those relying on a physical solvent should
be considered where distillation of the acid gases from the sour

21-29
gas is used in the process scheme to reduce the load on or in behavior of acid gas mixtures is complex, and careful consider-
some cases eliminate the solvent. ation must be given to the design of the project.69,70

SPREX® There have been a number of successful acid gas injection

projects, with sulfur contents from as little as 1 to more than
In the Sprex® process developed by IFP with Total and mar- 1500 tons per day.
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 LIQUID HYDROCARBON TREATING
column with a cold reflux from a downstream cold box. The acid
gas is separated as a pumpable liquid at line pressure and am- Most gasoline and LPG streams contain sulfur in various
bient temperature. A demonstration plant was built and started forms. LPG & raw NGL streams also can contain carbon diox-
up in 2005 to commercialize the technology. ide. Especially objectionable are hydrogen sulfide, mercaptans,
and elemental sulfur. Gasoline containing hydrogen sulfide has
Bulk Fractionation an objectionable odor and is corrosive. Mercaptans give an ob-
jectionable odor to gasoline and elemental sulfur makes the
Another technique than can be employed is bulk fraction-
gasoline corrosive. Carbonyl sulfide in the LPG can hydrolyze
ation or distillation of acid gases from the inlet feed. As dis-
and cause the product to become corrosive. A product contain-
cussed in Chapter 16 direct distillation of the CO2 from the inlet
ing the objectionable materials can be treated to remove the hy-
natural gas is limited by the CO2 solidification zone to about 15
drogen sulfide, carbonyl sulfide, and elemental sulfur and to ei-
mol% CO2 in the product gas.
ther remove the mercaptans or convert them to less objectionable
Further treatment of the residue gas requires an additional compounds like disulfides.
processing step to meet typical sales gas specifications or the
use of a solidification suppression additive (Ryan/Holmes Pro- NOTES ON LIQUID/LIQUID TREATING
cess) as described in Section 16 or the use of the CFZ® being
commercialized by ExxonMobil (See Emerging Technologies). Mixing
Good mixing of gasoline and treating solution may be ac-
PROCESS SELECTION complished by means of a low efficiency (40%) centrifugal pump.
Selection of the best technology to apply to a given gas The gasoline stream and solution recycle stream join just ahead
stream depends on many factors, and should be done by expe- of the pump and are discharged to the solution settling tank.
rienced personnel. Among the factors to be considered are: feed
Treaters may use static in-line mixers to obtain good gaso-
temperature and pressure, type and concentration of impuri-
line-caustic contact. A properly designed in-line static mixer
ties, desired gas specification, flow rate, location, operating ex-
will create a controlled droplet size with a narrow size distribu-
pense, and overall cost. Despite the large number of parameters
tion. Continuous renewal of the dispersed phase surface area
involved, it is possible to give some general guidelines as to
accelerates mass transfer. The static mixer accomplishes this
which process is most appropriate. For example, physical sol-
vents will generally be more attractive than chemical solvents uniform dispersion with less energy than most other devices. As
when the partial pressure of acidic components is high, owing to the velocity through the static mixer increases, the pressure
the higher loading and lower regeneration energy requirements drop increases and the mean droplet diameter decreases. A ho-
associated with a physical solvent. If heavy hydrocarbons are mogeneous mix is usually achieved in a mixer which is a few
present, however, physical solvents may be less attractive due pipe diameters in length.71
to their tendency to co-adsorb these contaminants.
Treated Product Clean-up
Fig. 21-26 shows an example solvent process selection chart
Sand towers may be placed downstream of a liquid wash of
for the case where both H2S and CO2 are to be removed from the
gasoline or LPG to remove any entrained water or solution. The
gas stream. This is a modified version of a graph taken from
gasoline flows downward through the tower. The design of the
Tennyson and Schaaf31 who also presented cases for removal of
tower is based on a space velocity of (4 volumes of gasoline)/
only H2S, only CO2, and selective H2S removal. Note that spe-
(volume of sand)/hour.
cific conditions may dictate the use of a process different from
what is presented in this type of chart.67 A downstream water wash of the treated hydrocarbon liquid
is also a good way to remove entrained water-based treating so-
ACID GAS INJECTION lutions such as caustic and amine. The process is identical to
the caustic wash shown in Fig. 21-27. A water circulation rate
In some cases, it is possible to compress the acid gas as gen- of 10 to 30 percent of the hydrocarbon rate should be adequate,
erated from a chemical or a physical solvent process and inject if good liquid-liquid contact is obtained. The solution concentra-
it into a depleted, non-producing, or even a producing reser- tion in the wash water should not build up to more than 3
voir68. A key consideration is the phase behavior of the acid gas weight percent.
mixture. Depending on temperature, pressure, and composi-
tion, the acid gas may be injected as a liquid or gas; or as a
Counterflow Contact Towers
dense phase. Dehydration is usually necessary to avoid corro- In the liquid/liquid contact tower, the hydrocarbon feed is
sion or hydrate formation. However, in many cases, a minimum usually introduced through a distributor at the bottom of the
in water-holding capacity occurs with respect to pressure Thus, tower and becomes the dispersed phase. The treating solution is
it may be possible to compress the gas to a given level, cool it, introduced counter currently at the top of the tower and be-
and drop out the liquid water. Further compression increases comes the continuous phase. The dispersed phase migrates up-
the capacity of acid gas to hold water, so that water drop out ward through the packing due to the difference in densities of
should not occur in the downstream piping or well. The phase the two liquids. The sweetened product is removed from the top

21-30
of the tower where 8 to 10 feet of open column are provided for The packing diameter should be no larger than one-eighth of
disengagement of the heavy phase. the tower diameter, but normally no smaller than one-half inch.
The hydrocarbon velocity should be about 15 GPM per square
Counterflow contact towers can either be packed or trayed. foot of open tower cross sectional area.72 The hydrocarbon dis-
A sieve (perforated) tray with downcomers is probably the most tribution nozzles should be designed with an orifice velocity in
effective for use in liquid-liquid contact devices. The light liquid the range of one ft/sec. Higher velocities result in the formation
flows through the perforations of each plate and is thereby dis- of small droplets which can form a hydrocarbon emulsion in the
persed into drops which rise through the continuous phase. The treating solution leaving the bottom of the tower.73
continuous liquid flows horizontally across each plate and pass-
es to the plate beneath it through the downcomer. If the heavy For caustic treaters, the packing material is usually carbon
liquid is the dispersed phase, the same design may be used but raschig rings, which offer better resistance to attack by the
turned upside down. Extraction rates are enhanced by the re- caustic solution.
peated coalescence and re-formation of droplets of the dispersed
phase. Hydrogen Sulfide & Carbon
For best tray efficiency, the dispersed phase must issue Dioxide Removal
cleanly from the perforations. This requires that the material of Hydrogen sulfide and carbon dioxide can be removed from
the plates be preferentially wetted by the continuous phase or LPG and gasoline by liquid-liquid contacting processes using a
that the dispersed phase issues from nozzles projecting beyond caustic solution, aqueous alkanolamines, or solid KOH. The
the plate’s surface. This may be formed by punching the holes caustic wash processes are described later. The alkanolamine
and leaving the burr in place, or otherwise forming the jets. The processes were described earlier in the gas treating section. For
liquid flowing at the larger volume rate should be the dispersed application, both a coalescer and a full flow carbon filter should
phase. be used to minimize the introduction of hydrocarbons into the
Perforations are usually 1/8 in. to 1/4 in. diameter with a to- regeneration section of the amine unit.
tal hole area equal to 15 to 25 percent of the column cross-sec- When treating hydrocarbon liquids with amine, contacting
tional area. The tray has no outlet weir. Perry provides a calcu- is generally accomplished in a liquid-liquid contactor, though
lation procedure for designing liquid-liquid contact sieve stirred reactors can be used. The tower should have a minimum
trays.72 of 20 feet of packing. The design flow rates for packed towers
Metal or plastic ring packing also provides good solution should not exceed 20 gpm liquid per square foot of cross section-
contact in counterflow towers. One theoretical stage can gener- al area.
ally be obtained in 6 to 8 feet of packed bed height. Ceramic or
steel packing should not be preferentially wetted by the dis- Minimizing Amine Losses
persed (hydrocarbon) phase. Previous investigations of wetting Minimizing losses of amine to liquid hydrocarbon streams
properties in liquid extraction applications generally indicate exiting the top of liquid treaters is a concern for operations.
that where the dispersed phase wets the packing, mass transfer Small amounts of amine in the treated liquid hydrocarbon can
efficiency is reduced.73 result in a significant increase in chemical costs in the down-

FIG. 21-26
Process Selection Chart for Simultaneous Removal of H2S and CO228

21-31
stream conditioning processes. Several studies have been con- Mercaptan Treating
ducted about solubility as it is one of the factors involved to
quantify amine entrainment. Other factors are disengagement Mercaptans can be converted to disulfides or removed from
time, emulsion formation and phase equilibrium. Water wash- liquid hydrocarbons by several methods. The method or combi-
ing of treated LPG streams can cut 99% of the amine losses. nation of methods that can be used depends on the mercaptan
content of the product to be treated and the specification that
Fig. 21-27 shows a suggested installation arrangement with must be met.
a pumparound set-up. Water from a circulation pump is inject-
ed through a quill to the treated LPG stream. A static mixer Carbonyl Sulfide Removal
immediately downstream will promote intimate contact be-
tween the two phases before they enter a settling vessel. This Carbonyl sulfide (COS) can hydrolyze and cause sweet LPG
vessel should provide 15 to 20 minutes residence time, be to become corrosive. Because of this issue and as the concern for
equipped for interface level control and probably use a boot to minimizing total sulfur emissions has increased, there has been
help separation of the aqueous phase, whose flow rate is nor- increased interest in removing COS from propane and LPG
mally much smaller than the hydrocarbon flow. streams. Several alternative processes can be used. COS can be
removed sacrificially by MEA. Mick74 has reported successful
Recommended water circulation flow is 3 gallons per barrel use of a combination of potassium hydroxide and methanol;
of treated LPG. The settling vessel can be equipped with inter- however, this process is sacrificial. The Malaprop75,76 process
nals to help coalescing small droplets, and thus reduce the re- uses DGA® and requires little or no modifications in the pro-
quired residence time and consequently the equipment volume. cess flow from that used for gas treating. The ADIP77 process
As the water exiting the bottom boot of the vessel is pumped utilizes aqueous DIPA. Molecular sieves can also be used for re-
back in a closed loop, the concentration of amine increases. The moving COS. The Malaprop, ADIP and molecular sieve process-
recommendation is to maintain an amine concentration in wa- es are all regenerative.
ter of 2.5 to 3 %w, therefore it is necessary to purge and make
up. The make up flow should be set monitoring the amine con- LIQUID HYDROCARBON TREATING
centration, and the purge flow should be controlled by the inter-
face level controller of the vessel. PROCESSES
A white paper developed by members of GPA’s Technical Molecular Sieve
Section A (Facilities Design), titled, “Design Considerations for
Water Wash Installations”, may be obtained from GPA for a Molecular sieve based sweetening system can handle large
more in depth description of this system and possible design or small streams. This process reduces total sulfur content by
alternatives. removing hydrogen sulfide, mercaptans, and partially remov-
ing organic sulfur in a vessel filled with molecular sieve adsor-
Sulfur Removal bent. It will produce 1A copper-strip, doctor-sweet product. In
addition, this process can be used to simultaneously dry the
Elemental sulfur is removed from the gasoline by contacting LPG in the same step with additional equipment if sufficient
it with a polysulfide wash solution. The solution is made up by bed capacity is included for this service.
using the following amounts of chemicals per 1,000 gallons of
water: 1,000 lb. of caustic (NaOH), 800 lb. of commercial Na2S, The largest drawback as in gas sweetening is that it is lim-
and 20 lb. of sulfur. The sodium sulfide (Na2S) is melted in a vat ited in the amount of impurity that can be handled due to the
by use of a steam lance. Add the sulfur to the melted Na2S. The low capacity of the sieve to adsorb impurities. In addition, this
sulfur must be completely dissolved in the liquid sulfide, and process requires secondary processing to sweeten the gas used
then this mixture is added to the 10% (1,000 gal. water and for regeneration, blending into fuel or other product stream
1,000 lb. NaOH) caustic solution. Protective clothing and gog- where sulfur level can be tolerated or a recycle upstream of an-
gles should be worn when handling these chemicals. other processing unit, which will remove the sulfur compounds
present in the gas.

Regenerative Caustic
FIG. 21-27 The regenerated caustic method of removing methyl and
Treated LPG Water Wash Schematic ethyl mercaptans from LPG or butane employs countercurrent
contacting of the liquid with 10% sodium hydroxide solution in
a packed column, and is suitable for handling a large hydrocar-
bon flow rate, while producing a doctor-sweet product. A typical
flow scheme is similar to the scheme for gas treating as illus-
trated in Fig. 21-19. The caustic is regenerated in a stripping
column by the addition of open steam or by steam internally
Lean
generated by a column heating element. A condenser may be
Amine Water Make-up used to condense water vapors that go overhead with the liber-
ated mercaptan vapors. The condensate is returned to the strip-
ping column to maintain caustic concentration. An LPG stream
Sour
containing 300 ppmw mercaptan sulfur can be treated doctor
LPG sweet with volume ratios of hydrocarbon to caustic as high as
Rich
Purge to Flash Tank or 33 to 1. Approximately six pounds of process steam per gallon of
Amine Regeneration
Amine caustic are required for regeneration at this hydrocarbon/caus-
tic volume ratio. The following ratios may be used to determine
optimum plant design:

21-32
 lb steam • Thiolex uses caustic to extract hydrogen sulfide and mer-
4 5 6 7 8 10 12 14.5 17 captans from fuel gas, propane, butane, alkylation feed
gal. NaOH
and straight run gasolines. Regen uses air to regenerate
gal. hydrocarbon Thiolex caustic solutions for reuse.
15 25 33 39 43 50 55 60 62
gal. NaOH

Highly corrosive conditions that can exist in a unit for this

Perco Solid Copper Chloride Sweetening
process are minimized by careful attention to operation condi- The PERCO® copper chloride sweetening process can be
tions, specifically by minimizing the contamination of the re- used to sweeten a wide range of NGL, straight run gasoline
generated caustic system with sodium sulfide and by operating streams and to a lesser extent kerosene to produce a doctor-
the rectifying column at low pressure and temperature. The sweet product. It is a continuous process in which the mercap-
maximum desired steam temperature to the reboiler is 260°F. tan sulfur in the gasoline is converted to disulfides over a cop-
The sulfide contamination is controlled by caustic washing of per catalyst. The PERCO® process and catalyst was originally
the LPG ahead of the mercaptan extractor and by blowdown of developed by Phillips Petroleum Co. and is now offered and sup-
the circulating solution. A maximum Na2S content of 0.2% is ported by Chemical Products Industries, Inc.
suggested.
The PERCO® catalyst is offered as a stationary bed of 6x30
The diameter of the extractor is based upon the hydrocar- mesh granular material. As manufactured, this material con-
bon throughput. A typical design uses flow rates of 10-15 tains approximately 10-25% water content. The catalyst loses
GPM/sq ft of cross-sectional area for a column packed with 1- its reactivity below 7% water content and above 30% the copper
1/4 in. raschig rings. Other tower packing may be used and, chloride can be extracted from the granular support. Adjust-
if so, the above throughput would be changed. The packed ment and/or addition of water content into the feed is generally
height is normally about 30 feet in two or three packed sec- not required. The PERCO® process can be run over a broad
tions to optimize dispersion of the hydrocarbon phase. An temperature range, ambient to 150ºF, optimally 120ºF to 130ºF.
additional 8 10 feet of column height is required for distribu- This is convenient for two reasons:
tion and settling areas. • It is about the same temperature as typical C4 splitter
® bottoms.
Merox
A variation of regenerated caustic process has been devel- • It is sufficiently high enough to prevent free water from
oped by UOP Process Division. Sour product is treated with condensing in the reactor.
caustic containing Merox catalyst to extract the mercaptans. Any hydrogen sulfide in the gasoline must be removed by a
The Merox solution is regenerated by mixing with air and oxi- scavenger, caustic wash or other means before contact with the
dizing. Disulfides and excess air are removed overhead. Exist- PERCO® bed.
ing extraction equipment with steam regeneration can be
adapted to the Merox process. In the sweetening reaction mercaptans are oxidized to the
disulfide and copper is reduced from cupric to cuprous. The cu-
The Merox solution gives a very high degree of removal of prous salt is simultaneously oxidized to a cupric salt by adding
mercaptans in a liquid stream. If more complete removal is de- air to the inlet gasoline stream.
sired, Merox also provides a fixed-bed catalytic conversion of
mercaptans to disulfides. These disulfides will not be removed The recommended charge rate is based on 1.5 volumes of
from the liquid stream, but will remain with the liquids. How- gasoline/packed volume of catalyst. Air is added to the sour
ever, the sulfur leaves as disulfide (low odor) rather than as charge by means of a diffusing disc at the rate of 1 cu ft of air
mercaptans. (STP)/bbl of charge for each 0.01% mercaptan sulfur. If the mer-
captan content of the gasoline is high, the operating pressure
Merichem® must be increased to hold the additional air in solution. The
rate of air injection should be maintained as near to this figure
Merichem®78 offers several processes for the removal of Na2S as practical since insufficient air will prevent complete oxida-
and/or mercaptans from light hydrocarbon liquids. In all of tion of the cuprous salt to the cupric salt. This will create a situ-
these the key technology is use of a patented Fiber Film® bun- ation where the copper in the catalyst is extracted into the hy-
dle to achieve intimate contact between the hydrocarbon feed drocarbon phase since the cuprous salt is soluble in this
and the caustic solution. The bundle is comprised of long con- media.
tinuous small diameter fibers placed in a pipe. The caustic solu-
tion preferentially wets the fibers, creating a large interfacial Also, excess air may result in airbinding of the treater vessel
area for contact with the hydrocarbon liquid. The fiber bundles and create an extremely hazardous condition. Also need to min-
can be installed easily into existing systems. imize excess regeneration oxygen, which may cause corrosion
downstream of bed. Gasoline with components that may be af-
• Merifining uses caustic to extract organic acids, mercap- fected by oxygen, such as olefins, should not be treated with this
tans, and other sulfur compounds from catalytic cracked process.
hydrocarbons.
• Napfining extracts naphthenic and other organic acids Solid Potassium Hydroxide
from petroleum distillates that produce kerosene and jet This process has low installation and operation costs. It will
fuel. desiccate as well as remove sulfur compounds. It is designed for
• Mericat uses an oxidation catalyst bearing caustic solu- removing trace amounts of H2S.
tion nd air to oxidize gasoline and kerosene mercaptans
to disulfides.

21-33
 NON-REGENERATIVE TREATING Centrifugal pumps used in caustic circulation may experi-
ence premature seal failure which results from crystallization
Caustic Wash of sodium hydroxide on the seal face. Using an API Plan 62 (ex-
ternal fluid quench) system with a fresh water seal flush fluid
Caustic wash can also be used to remove hydrogen sulfide or a Plan 52 (tandem seal) system with a buffer fluid are good
and/or lighter mercaptans from LPG and gasoline without re- solutions. Glandless pumps (such as magnetic drive and canned
generating the caustic for re-use. Liquid hydrocarbon and recir- motor) are also used in this application.
culated caustic (Ratio 2:1) are mixed by means of a pump or
static mixer and discharged to a settling tank where the liquids A method for calculating the acid (H2S and RSH) removal
separate. The size of the tank required is based on the retention efficiency in a batch caustic wash system was published by Bey-
time necessary for complete separation of the gasolinecaustic chok in 197380, but is no longer included in this chapter. It is
emulsion. The retention time varies from 1-1/2 hours for heavy shown in detail in the 11th edition GPSA Engineering Databook
gasolines to 30 minutes or less for propane. A coalescing ele- as Example 21-3.
ment on the settling tank inlet can reduce the required reten-
tion time. Since the separating tank is one-third full of caustic, OFFSHORE DESIGN CONSIDERATIONS
the liquid hydrocarbon retention time is based on two-thirds of
the tank volume. A typical caustic wash system utilizing a stat- Hydrocarbon Treating in the offshore industry encompasses
ic mixer is given in Fig. 21-28. many of the same processes as can be seen in the onshore indus-
try. However, much more emphasis is given to minimize size
Any discussion on materials of construction for caustic must and weight of the equipment. For floating production certain
take personnel safety into consideration for every application precautions also need to be taken in order to mitigate the nega-
Caustic solutions, especially when hot, are extremely damaging tive influences of the vessel movements. Of particular impor-
to the human body. The materials selection decision must take tance is the constant tilt of any contacting and regeneration
into account potential personnel exposure and may dictate a towers, which will seriously deteriorate the performance of the
more costly but more reliable material. towers due to mal-distribution. References are made to Sections
Mild steel remains the most utilized material. It is effective 7 and 19, where the separators and fractionators /absorbers
in caustic solutions up to 50 percent concentration and at tem- face similar challenges.
peratures up to 150°F. Corrosion rates in the range of 15-25 Some key considerations of importance for a sound design of
MPY (depending on agitation, etc.) can be expected. Austenitic a hydrocarbon treating system on an offshore installation are:
Ni-Cr stainless steels, primarily type 304 and 316, are very re-
sistant to caustic in concentrations up to 50 percent and tem- • Use of sophisticated high tensile strength metallurgy,
peratures to about 200°F. since this will both reduce equipment weight and allow
for less maintenance. The reduced equipment weight is
Stress corrosion cracking (caustic embrittlement) has been due to reduced wall thickness when using high tensile
reported in laboratory testing79 at concentrations as low as 10 steels.
percent with temperatures of 210°F. Stress relieving of carbon
steel is recommended for most applications.

FIG. 21-28
Non-Regenerative Caustic

21-34
 • Use of compact contacting technology in order to save cations where low weight and foot print is a premium. It com-
weight and space. petes well with conventional scavenging processes as the H2S
containing solvent is regenerated and thus scavenger chemical
• Use of compact module-based units with great emphasis consumption is avoided.
on optimized piping lay-outs and integrated solutions in
order to save weight and space. Membranes for CO2 Removal from Liquid
• Emphasis on keeping a clean operating plant by Ethane
• Starting with a clean plant and degreasing before It has been verified in a pilot facility utilizing a full scale
first fill and after large revamps. membrane element, that membranes can be used to remove
CO2 from a liquid ethane stream. The membrane module con-
• Keeping the feed gas clean by proper pretreatment. sists of an asymmetric hollow fiber made of cellulose-acetate.
• Maintaining a clean solvent by proper solvent filtra- Tests have shown acceptable ethane losses, while providing a
tion with both charcoal and mechanical filters and secondary benefit of removing some methane from the ethane
minimizing use of additives like anti foam agents. product82.

• Keeping a clean system by avoiding hydrocarbon Controlled-Freeze Zone® (CFZ®) Process

condensation in the absorber by superheating the
This ExxonMobil process removes CO2, H2S, and other im-
feed, if retrograde properties exist, insulating the
purities from natural gas. The unique aspect of the process is
contactor, and/or keeping a safe differential temper-
ature between liquid inlet and gas inlet (typically that it induces CO2 freezing in an open area of a cryogenic frac-
20°F higher on liquid side). While desirable onshore, tionation column83. (The Ryan Holmes process, described in
keeping a clean operating plant is much more impor- Section 16, adds a hydrocarbon stream to suppress CO2 freezing
tant offshore, because of the great difficulties of in the distillation column.) The solid CO2 melts in the stripping
“trucking” in huge reclaiming equipment and other section of the CFZ column, and flows out as a liquid along with
remediative equipment81. the other contaminants. The liquid stream can then be easily
pumped for downhole disposal. Methane, nitrogen, and helium
• Well equipped offshore laboratory with skilled personnel come out overhead.
is very important, since there is more incentive for prob-
lems that require troubleshooting to be solved on-site. CryoCell® Process
• Special considerations for floating production units This process83 offered by Cool Energy is a new technology for
should include: the removal of CO2 from CO2 rich feed gases. In the process de-
hydrated feed gas is cooled to a temperature just above the
• Avoiding greater constant tilt than 1 degree. freezing point of the CO2 through as combination of heat ex-
• Keeping vessel movements to a minimum with full change and refrigeration. The gas is flashed into a vessel where
dampening often required. the CO2 solidifies and separates from the gas phase. The solids
are then remelted to recover the CO2 as a liquid.
• Careful level measurements, see also Section 7.
Fast Cycle Pressure Swing Adsorption
• Marinized internals selection; for example, use of
pressurized liquid distribution in the absorber and Some rapid cycle pressure swing adsorption installations
regeneration towers. 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- REFERENCES

ly developed technologies in hydrocarbon treating which have
not yet seen full scale industrial applications, but have been 1. MSDS Number 100.240-4, March 1986.
subject of past GPA and Laurance Reid Gas Conditioning con- 2. National Safety Council Data Sheet 1-682-80.
ferences and/or publications worldwide. In future editions of
the GPSA Engineering Data Book, some of these emerging 3. Kathib, Z., “Reduction of Entrainment of Aerosols,” presented at the
technologies will be placed along with the industrial ones al- Laurance Reid Gas Conditioning Conference, University of Oklaho-
ready described in the main text, while newer technologies ma, March 1997.
emerge to be mentioned first here. 4. Herrin, J.P., “ Removing Very Fine Iron Sulfide Particles from Nat-
ural Gas,” presented at the Laurance Reid Gas Conditioning Confer-
The text which follows is in the order of subject appearance ence, University of Oklahoma, March 1994.
in the main text, starting with chemical reaction processes and
ending with batch processes. Understandably, it is beyond the 5. Stiltner, J., “Mercury Removal from Natural Gas and Liquid
scope and intent of this data book to cover every emerging tech- Streams,” proceedings of the 81st GPA Annual Convention, Dallas,
nology worthy of mention. Texas, March 2002.
6. Cameron, C.J., Barthel, Y. and Sarrazin, P., “Mercury Removal
Compact Amine Processes from Wet Natural Gas,” proceedings of the 73rd GPA Annual Con-
vention, New Orleans, March 1994, p. 256.
A compact amine process (ProCAP) has been developed by
ProPure AS. It is a continuous selective trace H2S removal pro- 7. Kensell, W.W., “How to Pick a Treating Plant,” Hydrocarbon Pro-
cess. It relies on the rapid and selective tertiary alkanolamine cessing, August 1979, p. 143.
chemistry with H2S used in a novel co-current short residence 8. Goar, B.G. and Arrington, T.O., “Guidelines Set for Handling Sour
time contactor. The process is ideally suited for offshore appli- Gas,” Oil and Gas Journal, June 26, 1978, p. 160.

21-35
9. Bottoms, R.R., U.S. Patent 1,783,901 (1930). 32. Kutsher, G.S., Smith G.A., and Greene, P.A., “Sour Gas Scrubbing-
Allied Chemical Solvent Process,” Proceedings of the 46th NGPA
10. Kohl, A.L. and Reisenfeld, F.C., Gas Purification, McGraw-Hill
Annual Convention, March 14-16, 1967, Houston, TX.
Book Co., Inc. (1960) (Chemical Engineering Series).
33. Hegwer, A.M. and Harris, R.A., “Selexol Solves High H2S/CO2 Prob-
11. Maddox, R.N, Gas and Liquid Sweetening, Campbell Petroleum Se- lem,” Hydrocarbon Processing, Vol. 49, No. 4, April 1970, p. 103.
ries, April 1977, p. 99.
34. Kohl, A.L. and Miller, F.E., U.S. Patent 2,926,751, March 1, 1960.
12. Lee, J.I., Otto, F.D., and Mather, A.E., “The Solubility of Mixtures of
CO2 and H2S in DEA Solutions,” Canadian J. Chem. Eng., 52, p. 125 35. Mak John et al, “Advances in Fluor Solvent Technology,” Proceed-
(1974). ings of the 89th Annual GPA Convention, 2010, Austin, TX.
13. Ballard, D., “How to Operate an Amine Plant,” Hydrocarbon Proc- 36. Laborie G., Cadours R., Barreau A., and Lecomte F., “IFPEXOL: An
essing and Petroleum Refining, Vol. 45, No. 4, April 1966, p. 137. Attractive Solution for RSH and COS Removal From Natural Gas”,
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GPA RESEARCH REPORTS
66. Lallemand, F. and Minkkinen, A., ”Highly Sour Gas Processing in
an Ever-Greener World,” Proceedings of the 80th Annual GPA Con- Listed below are GPA Research Reports that deal with
vention, March 2001, San Antonio, TX amine enthalpies, acid gas equilibrium and other topics cited in
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High CO2 Content,” 61st Annual GPA Convention, March 1982. Report Title
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RR-85 Enthalpies of Solutions of CO2 in Aqueous Diglycolamine®
Acid Gas Disposal without Dehydration” proceedings of the 78th
GPA Annual Convention, March 1999, Nashville, TN Solutions Scott P. Christensen, James J. Christensen and
Reed M. Izatt, Brigham Young University, Provo, Utah.
69. Lock, B.W., “Acid Gas Disposal: a Field Perspective,” proceedings of Project 821-84.
the 76th GPA Annual Convention, March 1997, San Antonio, TX
RR-102 Enthalpies of Solution of CO2 in Aqueous Methyldieth-
70. Carroll, J.J. and Maddocks, J.R., “Design Considerations for Acid
anolamine Solutions Keith E. Markley, James J. Chris-
Gas Injection,” Laurance Reid Gas Conditioning Conference, Nor-
man, Oklahoma, March 1999. tensen and Reed M. Izatt, Brigham Young University,
Provo, Utah. Project 821.
71. Koch Engineering Company, Bulletin KSM-5, 1986.
RR-104 Equilibrium Solubility of Carbon Dioxide or Hydrogen-
72. Perry, R.H. and Chilton, C.H., Chemical Engineer’s Handbook, 5th Sulfide in Aqueous Solutions of Monoethanolamine, Dig-
Edition, McGraw Hill Book Co., NY, 1973, p. 21-19. lycolamine, Diethanolamine and Methyldiethanolamine
73. Russell, Richard M., “Liquid-Liquid Contactors Need Careful At- R.N. Maddox, A.H. Bhairi, James R. Diers and P.A. Tho-
tention,” Oil & Gas Journal, December 1, 1980, p. 135 mas, Oklahoma State University, Stillwater, Oklahoma.
Project 841.
74. Mick, M.B., “Treat Propane for COS Removal,” Hydrocarbon Pro-
cessing, July 1976, p. 137. RR-108 Enthalpies of Solution of CO2 in Aqueous Diethanolamine
75. McClure, G.P. and Morrow, D.C., “Amine Process Removes COS Solutions Rebecca Helton, James J. Christensen and
from Propane Economically,” Oil and Gas Journal, July 2, 1979, p. Reed M. Izatt, Brigham Young University, Provo, Utah,
107. Project 821-86.

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RR-114 Enthalpies of Solution of H2S in Aqueous Diethanolamine RR 152 Physical Properties of MEA, DEA, MDEA and MDEA
Solutions Rebecca Van Dam, James J. Christensen, Reed Based Blends Ralph W. Weiland, Optimized gas Treat-
M. Izatt, and John L. Oscarson, Brigham Young Univer- ing Inc. Houston, Texas. Project 911.
sity, Provo, Utah. Project 821.
RR 153 Enhanced Factors for Acid Gas Removal with Single and
RR-124 Equilibrium Solubility of CO2 or H2S in Protonated Solu- Mixed Amines Ralph W. Weiland, Optimized gas Treat-
tions of DEA at Low Partial Pressures R. N. Maddox and ing Inc. Houston, Texas. Project 911.
E. M. Elizondo, Oklahoma State University, Stillwater,
RR-180 Amine BTEX Solubility Valtz, A., et al; Project 9171;
Oklahoma. Project 841.
2002
RR-125 Equilibrium Solubility of CO2 or H2S in Protonated So- RR-185 Solubility of Hydrocarbons in Amine Solutions Valtz, A.,
lutions of DEA R. N. Maddox, M. Abu-Arabi and E. M. et al; Project 011; 2004.
Elizondo, Oklahoma State University, Stillwater, Okla-
homa. Project 841. RR-195 Mokraoui, S., et al; GPA Research Report, RR-195; Mutu-
al Solubility of Hydrocarbons in Amine Solutions; Project
R-127 Enthalpies of Solution of H2S in Aqueous Methyldieth-
021; 2008.
anolamine Solutions J. L. Oscarson, and R. M.Izatt,
Brigham Young University, Provo, Utah. Project 821. RR-201 Oxygen Removal from Natural Gas Systems
RR-206 Solubility of Hydrocarbons in Amine Solutions (Draft) D.
RR 151 Reaction Kinetics of CO2 with MEA, DEA, and MDEA
Mamrosh et al; Project 975-5; 2011 Planned
and in MDEA Based Blends Ralph W. Weiland, Opti-
mized gas Treating Inc. Houston, Texas. Project 911. TP-29 Critchfield, J., et al; Hydrocarbon / Water and Hydrocar-
bon / Aqueous Amines Mutual Solubility; 2003.

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