GAS SWEETENING

There are more than 30 natural gas sweetening

processes that can be classified as:
Batch processes, e.g., iron sponge, Chemsweet, Sulfa-Check,
and caustic soda. Because the reactant is discarded, the use
is limited to removing small amounts of sulfur, i.e., low gas
flow rates and/or small concentrations of hydrogen sulfide.
Aqueous amine solutions: monoethanolamine, diethanolamine, diglycolamine, methyldiethanilamine, and proprietary
formulations such as Amine Guard, Ucarsol, Flexors, and
Gas/Spec. These solutions are regenerated and are used to
remove large amounts of sulfur, and CO2 when needed.

Mixed Solutions (mixtures of amine, physical solvent & water):

Sulfinol, Flexors, and Optisol. These solutions also absorb
organic sulfur and are capable of high acid gas loadings.

 Physical Solents: Selexon, Rectisol, Purisol, Fluor Solvent are

used for bulk removal of CO2 frequently offshore. These can
be regenerated without heat and simultaneously dry the gas.
Hot potassium carbonate solutions: Hot Plot, Catacarb,
Benfield and Giammarco-etrocoke are chemical analogs of the
physical solvents.
Direct oxidation to sulfur: Stretford and Sulferox Lo Cat
practically eliminate H2S.
Adsorption: Linde, Zeochem,and Davison Chemical molecular
sieves, which is limited to low acid gas concentrations, and the
gas is simultaneously dried.
Membranes: A VIR, Air Products, Cynara (Dow), duPont,
Grace, International Permeation, and Monsanto are most
suitable for bulk CO2 separations, especially when the feedgas concentration is very high.

BATCH PROCESSES
ADVANTAGE

Complete removal of low to medium H2S concentrations

with no consumption of the reactant by CO2.
Relatively low capital investment when compared to
regenerative processes.
The affinity for sulfur-containing gases is largely
independent of the operating pressure.

Often the removal of organic sulfur contaminants such as

the lower molecular weigh mercaptans is adequate.

DISADVANTAGE
Uninterrupted operation requires two or more
contact towers, so that at least one tower is on
stream when another is being recharged.
The pressure of liquids-poor upstream separation or
condensation in the tower due to temperature
changes ruins iron sponge chips and makes liquid
sweeteners foam.
Hydrate formation can occur at higher pressures
and lower temperatures.

Process Descriptions
Iron Sponge
Iron sponge is the oldest and still the most widely used batch process
(Duckworth and Geddes, 1965; Anerousis and Whitman, 1985; and
Zapffe, 1963). Because the bed consists of solid particles, the
superficial gas velocity is higher and the tower diameter smaller than
for slurries.
Iron sponge consists of wood chips or savings impregnated with
hydrated ferric oxide, Fe2O3, and sodium carbonate to control the pH
major suppliers are Connelly-GPM and Physichem Technologies.
The chips are dumped into the vertical contact tower (Figure 2)
through the manway at the top.
The sweetened reactions: ferric sulfide, Fe2S3, ferric mercaptide
Fe2O3 + 3 H2S = Fe2S3 + 3 H2O
Fe2O3 + 6 RSH = 2 Fe(RS)3 + 3 H2O
Regeneration: 2Fe2S3 + 3O2 = 2Fe2O3 + 6S

Liquid and Slurry Processes.

Occasionally chemicals other than those described below are
acountered, but their use is limited by significant shortcomings.
Scavinox, and Di-Chem are mixtures of formaldehyde,
methanol, and water. They react with H2S to form cyclic
carbon-sulfur compounds known and formthionals.
Slurries of iron oxide have been used to selectively absorb H2S
(Fox, 1981; and Kattner et al., 1986).
The results have been inconsistent; problems include obtaining
stoichiometric use, premature H2S breakthrough, and foaming.
Also, high corrosion rates have been reported. This has been
circumvented by coating the contact vessels with phenolic or
epoxy resins (Samuels, 1988).

 Chemsweet is a NATCO process (Manning, 1979; and

Manning et al., 1981).
The white powder product is a mixture of zinc oxide, zinc
acetate, and a dispersant to keep the zinc oxide particles in
suspension.
When one part is mixed with five parts of water the acetate
dissolves and provides a controlled sources of zinc ions that
react instantaneously with the bisulfide ions that are formed
when H2S sulfide dissolves in water.
The zinc oxide replenishes the zinc acetate :
Sweetening ZnAc2 + H2S = ZnS + 2 Hac
Regeneration ZnO + 2 HAc = ZnS + H2O
Overall
ZnO + H2S = ZnS + H2O

A typical contact tower for liquids and slurries

The vessel is cylindrical with elliptical heads. It is equpped
with inlet and outlet gas nozzles, slurry feed and overflow
nozzles, a drain, a manway to meet code requirements, a
mist eleminator, and a gas distributor.
The sour gas enters at the bottom and rises to the
distributor plate where it is dispersed into small gas
bubbles.These rise through the slurry and provide the
agitation needed to keep the slurry mixed.

The sweetened gas flows through the mist eleminator and

leavesat the top.

Design procedure is recommended:

Required Data :
Gas flow rate, Q, MMscfd
Operating pressure, P, psig
Operating temperature, T, oF
H2S inlet concentration, (ppmv), If the H2S concentration is in
grains H2S/100 scf, multiply by 15.9 to get ppmv.)
Compressibility factor, Z (If gas gravity is not known use 0.7.)
Expansion factor, f (Use 1.10 to 1.20)
When the bubbles rise at 48 ft/min f is related to the supervicial gas velocity Vs in ft/min;
Vs = 48 (f 1)/f
Optimal Vs depend on the type of sweetening processes

Calculation Procedure:
Gas actual flow rate, Qa at T&P

19.63(Q)(T 460)( Z )
Qa =
( P 14.7)

acfm

Where 14.7 = atmospheric pressure at sea level

Internal cross-sectional area (A) & internal vessel diameter, ID.

Process
Iron Sponge
Chemsweet
Sulfa-Check
Caustic Soda

Superficial Velocity
ft/min
10.0
6.5
8.0
8.0

Cross Sectional
Area sq ft
0.10 Qa
0.16 Qa
0.11 Qa
0.13 Qa

ID = [A/0.7854]0.5 ft
Select a vessel OD that provides at least this internal diameter after
considering wall thickness. Calculate the actual ID (ft) and use this valve.

Calculate the daily chemical requirement.

Iron Sponge
IS = 0.0133 (Q)(ppmv H2S) ft3/day
Chemsweet
CS = 0.248 (Q)(ppmv H2S) lb/day
Sulfa-Check
SC = 0.0474 (Q)(ppmv H2S) gal/day
Caustic Soda Depends on the CO2 content
NaSH: NS = 0.109 (Q)(ppmv H2S) gal, 20% NaOH/day
Select a static bed heigh, L typically 10 to 20 ft.
The volume, RV, of reactant is :
RV = 07854 (ID)2(L) ft3
Note that bubbling gas into a liquid increases the volume (and the heigh in
the lower) by the volume of the gas bubbles in the liquid at any given time.
This increase in bath height up to 20% - must be considered in selecting
sell length of the lower.

 The bed life, BL, is :

Iron Sponge BL =
RV/IS days
Chemsweet BL = 11.7 RV/CS days
Sulfa-Check BL = 7.5 RV/SC days
The charge requirements are :
Iron Sponge : RV bushels
Chemsweet : 11.7 RV lb solids
RV gal water Sulfa-Check : 7.5 RV gallons
For iron sponge units the following checks are advisable even though
they seldom invalidate a design. Make sure the mass velocity is less than
78 (g)0.5 lb/min sq ft. This occurs only with liquid hydrocarbons and a
density over 30 lb/cu ft.
Check the contact time by determining the space velocity acfh/ft3 of bed.
This should be less than 180 acfh/ft3 for low H2S contents and 90 acfh/ft3
for over 50 gr/100 scf gas.
Check the heat effect. This sulfur deposition or absorption should be less
than 15 gr/min ft2 of bed area.

Example 1
Select & size sweetening process for gas stream 100 Mscfd, 100
ppm H2S, 1% CO2, 200 psig, 80 oF, SG=0.7, elevation =1000 ft.
First estimate sulfur content :
lb S scf lb mole gas mol H 2 S lb S 100,000 1
100 32

=
= 0.85
mol gas mol H S =
day day scf
1
379.5 1,000,000 1

Use a batch process select iron sponge. Design steps are :

At actual gas flowing conditions:
Z = 0.955

Patm = 14.2 at 1000 ft elevation

19.63 0.180 459.70.955

Qa =
= 4.72 acfm
200 14.2

 Assume superficial velocity is 2.5 ft/min.

Bed cross-sectional area = 0.4 Qa = 1.89 ft2
Bed diameter
= 1.5 ft ID
Daily chemical requirement
IS = (0.0133)(0.1)(100) = 0.133 ft3/day
Select bed heigh 5 ft, D = 1.5 ft; RV = (0.7854)(1.5)2(5)= 8.84 ft3
Bed life = RV/IS = 8.84/0.133 = 66 days
Check contact time:
Space velocity = acfh/RV = (4.72)(60)/(8.84) = 32 acfh/ft3
Okay because < 180.
Check heat effect
100 ppmv = 100/15.9 = 6.3 gr H2S/100 scf
S deposition = (scf/min)(gr H2S/scf)/(bed area)
= (100,000/24 x 60)(6.3/100)/(1.9)
= 2.3 gr H2S/min ft2 bed
Okey because less than 15 gr H2S/min ft2 bed.

Operation
The keys to trouble-free operating are proper installation of
the tower and preparation of the reactant. Be sure to :

1. Check the design parameters, especially the superficial

velocity of the sour gas.
2. Anticipate condensation and hydrate formation during
cold weather.
3. Include an inlet separator.
4. Pressurize the tower slowly and, if possible, from both
the top and bottom.
5. Unless impractical (e.g., remote areas), check the
operation daily.

 Iron Sponge :
1. For medium and large vessels, coarse packing can be
placed below the bed support to prevent collapse of the
support structure and possible damage to the vessel shell.
2. Make sure there is a strainer in the exit gas line to remove
entrained particles of iron sponge.

3. Install a differential pressure controller across the tower.

4. Check the condition of the iron sponge before loading.
5. Load sponge into vessel in incremental layers of one foot.

 Slurries
1. Check the water supply.
2. Check the pH of the batch.
3. Perform a foam test before starting the unit.
4. Make sure that the sour gas is saturated with water. If
not, add water periofically to restore the slurry level.
5. Include a downstream separator with a sight glass.

Trouble-shooting
The major problems are: premature H2S breakthrough;
rapid buildup of the pressure drop across iron sponge
beds; and foaming with bath carryover in slurries.
Iron Sponge :
1. Check the inlet gas temperature.
2. Check for channeling which usually occurs at very low gas
superficial velocities, i.e., below 2 ft/min.
3. Check for hydrate formation and condensation.
4. Check the alkalinity of the water in the bottom of the tower.
5. Check the pressure drop across the tower.
6. Find the cause of the liquids.
7. As a last resort back flow the bed to lift and repack the chips.

 Slurries:
1. Check the sour gas velocity in the contactor.
2. Check the inlet gas temperature.
3. Check the bath level.
4. Check the outlet H2S cocentration.
5. Check the pH of the slurry.
6. Check for hydrocarbon condensation.
7. Check for settling of the slurry.
8. Check the inlet gas for RSH, RSSR, and COS.
9. Check the distributor plate or sparger.

AMINE AND MIXED SOLUTIONS

The advantages of processes where the treating solution
is regenerated and re-circulated are :
1. Complete removal of medium to high concentrations of
acid gases even at high gas flow rates with negligible
consumption of the reactant.
2. Relatively low operating cost per pound of sulfur removed
as compared with batch processes.
3. The solution composition can be tailored to the sour gas
composition.
4. Large amounts of organic sulfure compounds can also be
removed when a physical solvent is added to the amine
solution.

 The disadvantages are :

1. High capital investment compared with batch processes.
2. The operational and maintenance costs are significant.
3. Some of the processes: Sulfinol and Flexors require
license or royalty fees.

Chemical Reaction
The reactions between amines and acid gases have been
examined extensively (Dankwerts, 1970; Deshmukh and Mather,
1981; Kent and Eisenberg, 1976; Moshfeghian et al., 1977).
Peotonation of the amine. RNH2, RRNH, and RRRN denote
primary, secondary, and tertiary amines, respectively and the
subtitution of one, two, and all three of the hydrogen atoms of the
parent ammonia molecule, NH3, with alkanol groups, for example,
with a primary amine: RNH2 + H+ = RNH3+
Reaction with H2S (RRNH). The addition compound between the
protonated amine and bisulfide ion can be formed by two parallel
mechanisms:
RRNH2+ + HS+ = RRNH2.SH
RRNH + H2S = RRNH2.SH

Chemical Reaction
The first reaction is fast, and together they limit the
formation of the sulfide addition compound:
2 RRNH2+ + S-- = (RRNH2).S
The rich solution is flashed at an intermediate pressure and
again at low pressure where it is also stripped with the
overhead vapors from the regenerator.

Most of this semi-lean solution is fed to the lower part of the

contactor. The rest is regenerated and fed to the top of the
contactor. The advantages are increased plant capacity and
less energy for regeneration.

Design:
Amine Flow Rate
1. Select the appropriate sweetening solution and the
concentrations of amine and physical solvent.
2. Calculate the partial pressure of H2S, CO2, RSH and other
organic sulfur gases using the tower pressure and the inlet
gas composition.
3. Estimate the temperature of the rich amine solution at the
bottom of the contact tower. This is usually 20 to 40 oF hotter
than the inlet gas.
4. Calculate the equilibrium loadings for H2S, CO2, RSH, etc., in
the rich amine solution.
5. Assume an approach to equilibrium and determine the
pickups for H2S, CO2, RSH, etc.
6. Calculate the amine circulation rate from the pickup and the
acid gas content of the sour gas.

7. Calculate the heats of reaction and solution for all of the

gas pickups. Use the data in Table 3 and the GPSA (1987)
Engineering Data Book.
8. Estimate the lean amine feed temperature 100 to 130 oF
and the sweet gas outlet temperature 15 to 30 oF
hotter than the inlet gas and/or 0 to 15 oF above the lean
amine.
9. Make a heat balance around the contact tower.
10. A quick estimate of the flow rate for typical MEA, DEA,
DGA and MDEA solutions can be obtained from the
following equation (based on Khan and Manning, 1985):
11. Circulation rate, gpm = K (MMscfd)(Mol percent AG
removed)

 Adsorption System
1. The high-pressure process gas system consists of an inlet
scrubber, contact tower, and outlet separator.
2. The inlet scrubber removes slugs and drops of condensed
hydrocarbons, produced water, corrosion inhibitors, and well
treating chemicals from the inlet sour gas stream.
3. Most adsorber towers use trays to contact the sour gas with the
amine solution.
4. The cross-sectional area of the contactor is sized for the gas and
amine flow rates. The maximum gas superficial velocity is obtained
from the Souders-Brown equation.
Vgas = 0.25 [(amine - gas)/gas]0.5 ft/sec.

5. Check the hydrocarbon dew-point in the contactor at both the inlet

and outlet conditions.
6. Check for retrograde condensation in the absorber tower.

 Regeneration System
1. The regeneration system consists of a flash tank,
rich/lean amine heat exchanger, stripping still, reboiler
filters, and aerial cooler.
2. The lean/rich amine heat exchanger preheats the rich
amine solution and reduces the duty of the reboiler.
Reclaimer
1. Primary amines require additional regeneration, i.e.,
semi-continous distillation in areclaimer (Fig. 6).
2. The reclaimer temperature rises as the contaminants
accumulate and operation is stopped at a predetermined
temperature 300 oF for MEA to limit thermal
degradation of the amine.

 Filters
Both mechanical filters for particulates and activated carbon
filters for heavy hydrocarbons and amine degradation
products are needed.
A mechanical filter in the rich amine line just after the flash
tank prevents plugging in the lean/rich heat exchanger and
still.
Including a carbon filter reduces the tendency to foam in
the still, but this adsorbs hydrocarbons that would otherwise
be removed in the still.
The mechanical filter should be full flow and remove 95% of
10 microns or large particles.

 Pumps
1. The amine booster and reflux pumps are centrifugal,
preferably in-line or horizontal, with TEFC motors.
2. In sizing and rating pumps use a low positive suction
pressure of 310 psig. Motor sizes can be estimated
from the amine circulation rate (Jones and Perry, 1973).
Motor

Horsepower

Circulation Pump

gpm x psig x 0.00065

Booster Pumps

gpm x 0.06

Reflux Pumps

gpm x 0.06

Aerial Cooler

gpm x 0.36

 Construction Materials
1. Pearce and DuPart (1985) and Richert et al. (1989) reviewed the types
of corrosion that occur in amine plants: general, galvanic, crevice,
pitting, intergranular, selective leaching, erosion, and stress corrosion
cracking.
2. In considering the susceptibility of steel to stress corrosion cracking the
key property is hardness. In addition to H2S corrosion, the following
factors must be considered :
3. CO2 corrosion, especially when the rich amine temperature exceeds 150
oF.
4. Electrolytic corrosion due to the presence of unlike netals in aqueous
environments.
5. Oxidation corrosion due to free oxygen in the makeup water ad feed gas
streams.

Operation
Plant Check Out
1. Check that all materials have been received and order
replacements for damaged items.
2. Install blinds on the inlet gas line to prevent accidental and
premature pressurization of plant.
3. Check assembly of plant.
4. Check mechanical equipment for lubrication, alignment, rotation,
etc. Pack pumps and put filter elements into filters.
5. Check calibration of pressure, flow, and temperature and level
instrumen. Pressure test vessels, pipes, etc., using water or
clean gas. Repair leaks.
6. Check the alarm and safety devices.
7. Remove blinds and establish fuel gas, instrument air, and power
supply.

 Clean Out of Amine Unit.

1. Charge the unit with 2% Na2CO3. Fire the reboiler and heat to 200 oF.
2. Check the circulation pump.
3. Start the reflux condenser fan.
4. Pressurize contact tower slowly.
5. Ven trapped air from valves at high points.
6. Estabilish an operating level in the contactor.
7. Circulate for six hours.
8. Shut off boiler and pumps and fans when system has cooler to 180 oF.
9. Drain the entire system. Use blanket gas at 2 psig to keep air out.
10. Refill the amine system with deionized water.
11. Repeat the wash-out procedure.
12. If clean, drain sufficial water to add enough amine to obtain the desired
solution strength.
13. Circulation for two hour to mix throughly.
14. Open the block valves on filters, close bypass valves.

 Troubleshooting
1.Gas is not Sweet
2.Amine solution not regenerated
3.Dirty, degraded amine
4.Excessive corrosion
5.Foaming of amine solution