29-Nov-14

Natural Gas Processing and Liquefaction

Acid Gas Treating
Chemical Absorption – Alkali Salts (Hot Potassium Carbonate) (1)
The process was developed originally for the removal of CO2. However, it can also
remove H2S if H2S is present with CO2. Special designs are required for removing H2S to
pipeline specifications or to reduce CO2 to low levels.
The process is very similar in concept to the amine process, in that after physical
absorption into the liquid, the CO2 and H2S react chemically with the solution. The
chemistry is relatively complex, but the overall reactions are represented by:

Several commercial trade names for the hot potassium carbonate process. Among which
are Benfield process and Catacarb process. The Benfield Process is licensed by UOP. Several
activators are used to enhance the performance of the potassium carbonate solution. On
the other hand, the Catacarb Process is licensed by Eickmeyer and Associates. Activators,
corrosion inhibitors, potassium salts, and water are contained in the solution. This process is
mostly used in the ammonia industry.

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Natural Gas Processing and Liquefaction

Acid Gas Treating
Chemical Absorption – Alkali Salts (Hot Potassium Carbonate) (2)
In a typical application, the contactor will
operate at approximately 300 psig (20 barg),
with the lean carbonate solution entering near
225°F (110°C) and leaving at 240°F (115°C).
The rich carbonate pressure is reduced to
approximately 5 psig (0.3 barg) as it enters the
stripper. Approximately one third to two thirds
of the absorbed CO2 is released by the pressure
reduction, which reduces the amount of steam
required for stripping.
The lean carbonate solution leaves the
stripper at the same temperature as it enters the
contactor, and eliminates the need for heat
exchange between the rich and lean streams.
The heat of solution for absorption of CO2 in potassium carbonate is small, and
consequently the temperature rise in the contactor is small and less energy is required for
regeneration.

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Natural Gas Processing and Liquefaction

Acid Gas Treating
Physical Absorption
During the physical absorption no chemical reaction occurs and acid gas removal depends
entirely on physical absorption. Some of the inherent advantages and disadvantages of
physical absorption processes are
 Absorption processes are generally most efficient when the partial pressures of the
acid gases are relatively high, because partial pressure is the driving force for the
absorption.
 Heavy hydrocarbons are strongly absorbed by the solvents used, and consequently acid
gas removal is most efficient in natural gases with low concentrations of heavier
hydrocarbons.
 Solvents can be chosen for selective removal of sulfur compounds, which allows CO2 to
be slipped into the residue gas stream and reduce separation costs.
 Energy requirements for regeneration of the solvent are lower than in systems that
involve chemical reactions.
 Separation can be carried out at near-ambient temperature.
 Partial dehydration may occur along with acid gas removal, whereas amine processes
produce a water saturated product stream that must be dried in most applications.

Dr. Tamer Samir © 164

Natural Gas Processing and Liquefaction

Acid Gas Treating
Physical Absorption – Selexol Process
The solvent used in Selexol process is dimethyl ether of polyethylene glycol
n = 2-9
Selexol has a preferential absorption of H2S more than CO2 The process can reduce
H2S to 4 ppmv, reduce CO2 to levels below 50 ppmv, and essentially remove all
mercaptans, CS2, and COS.
Selexol removes substantial quantities of NGLs, a feature that can be either positive or
negative, depending on the composition of the gas being processed and the desired
products.
Finally, Selexol provides dehydration since it absorbs water efficiently.
Unlike the amine systems, no irreversible products are generated in the process,
which thus eliminates the need for reclaiming.
The solvent has a higher viscosity which reduces mass transfer rates and tray
efficiencies and increases packing or tray requirements, especially at reduced
temperatures. Since it is sometimes necessary to reduce temperature to increase acid
gas solubility and reduce circulation rate, this could be a disadvantage.

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Natural Gas Processing and Liquefaction

Acid Gas Treating
Physical Absorption – Rectisol Process

The solvent used is methanol refrigerated to less than -30 oF (-35 oC).
Remove both CO2 and H2S and other sulfur components. Rectisol has preferential
absorption of H2S more than CO2 . More selective of H2S and slip CO2 can be done by
the addition of toluene to methanol solvent
Methanol has a relatively high vapor pressure at normal process conditions, so deep
refrigeration or special recovery methods are required to prevent high solvent losses.
At cold temperatures, methanol also has a high affinity for hydrocarbon constituents
of the gas streams. For example, propane is more soluble in methanol than carbon
dioxide.
Solubilities of H2S and COS in Methanol are higher than in Selexol
Higher capital cost. In addition, the supply of refrigeration at low temperatures
requires much power. However, this disadvantage can be outweighed by a considerable
reduction of the solvent flow rate as compared to other physical solvent processes

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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Introduction
The side stream from acid gas treating units consists mainly of H2S and/or CO2. CO2 is
usually vented to the atmosphere. H2S could be routed to an incinerator or flare, which
would convert the H2S to SO2. The release of H2S to the atmosphere is limited by
environmental regulations. In addition. SO2 results in what is called acid rains. In any
case, environmental regulations severely restrict the amount of H2S that can be vented
or flared.
The second way is to recover sulfur from H2S. Most sulfur recovery processes use
chemical reactions to oxidize H2S and produce elemental sulfur. These processes are
generally based either on the reaction of H2S and O2 or H2S and SO2. Both reactions
yield water and elemental sulfur. These processes are licensed and involve specialized
catalysts and/or solvents. These processes can be used directly on the produced gas
stream.
There are two common methods of sulfur recovery: liquid redox and Claus sulfur
recovery processes.

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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Liquid Redox (1)
Liquid redox sulfur recovery processes
are liquid-phase oxidation processes that
use a dilute aqueous solution of iron or
vanadium to remove H2S selectively by
chemical absorption from sour gas
streams.
These processes can be used on
relatively small or dilute H2S stream to
recover sulfur from the acid gas stream.
 The mildly alkaline lean liquid scrubs
the H2S from the inlet gas stream, and
the catalyst oxidizes the H2S to elemental
sulfur.
The reduced catalyst is regenerated by
contact with air in the oxidizer.
Sulfur is removed then from the
solution by flotation or settling,
depending on the process.
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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Liquid Redox (2)
Liquid redox sulfur recovery processes all share the following major operations:
1) Sour gas cleaning by absorption of H2S into a circulating alkaline solution

2) Conversion of the formed HS- to elemental sulfur via the action of an auxiliary redox
reagent

The last reaction shown is slow. The addition of an auxiliary redox reagent (ARR) increases
the rate of reaction and directs the oxidation to elemental sulfur.

The overall chemistry of liquid redox processes is:

Regeneration of the Spent ARR Using Air:

3) Separation and recovery of solid sulfur.

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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Claus Sulfur Recovery (1)
The Claus sulfur recovery process is the most widely used technology for recovering
elemental sulfur from sour gas.
The Claus process consists of the vapor-phase oxidation of H2S to form water and
elemental sulfur, according to the overall reaction:

The above overall reaction does not represent the reaction mechanism or show
intermediate steps. In practice, the reaction is carried out in two steps:

The first reaction is a highly exothermic combustion reaction, whereas the second is a
more weakly exothermic reaction promoted by a catalyst to reach equilibrium.

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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Claus Sulfur Recovery (2)
Second equation equilibrium conversion is represented in the figure

The melting point of amorphous sulfur is 248°F.

The Figure shows that the maximum conversion to sulfur is obtained at temperatures
near the melting point of sulfur.
However, it is desired to maintain sulfur above the dew point so that the sulfur does not
condense on the catalyst. However, this temperature does not operate at optimum
equilibrium conversion and it is not economical.
Instead, series of converters are used, with the sulfur product withdrawn from the
reacting mixture between converters. Withdrawing the sulfur product causes the reaction
to shift to the right, which results in more sulfur product.
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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Claus Sulfur Recovery (3)
The first reaction takes place
in a combustion furnace
operating at about 3 to 8 psig
and 1800 F (the exit is at 600 F
since it is cooled with BFW).
The air flow rate is adjusted to
react with 1/3 of the H2S
(why?), along with any other
combustibles, such as
hydrocarbons and mercaptans.
The H2S reaction is exothermic and is used to produce steam in a waste-heat boiler.
Both reactions take place in the furnace−boiler combination, and the gases exit the
waste-heat boiler in the range of 500 to 650°F, which is above the sulfur dew point, so no
sulfur condenses in the boiler

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Natural Gas Processing and Liquefaction

Sulfur Recovery Processes
Claus Sulfur Recovery (4)
The combustion
furnace−boiler is followed by
several catalytic reactors in
which only the 2nd reaction
takes place because all the O2
has been consumed in the
furnace.
Each catalytic reactor is
followed by a condenser to
remove the sulfur formed. The
gas is cooled to in the condenser to remove elemental sulfur. The condenser generally
achieves cooling by heat exchange with water to produce low-pressure steam.
Vapor that leaves the condenser is at the sulfur dew point, so the gas is reheated before
passing to the next converter to prevent sulfur deposition on the catalyst.

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Natural Gas Processing and Liquefaction

DehydrationCO
2

Sulfur Sulfur Acid

Recovery Unit Gas

Raw Gas Inlet Gas Acid Gas

Phase Separation
Compression Treating

Condensate to
Solids Water LNG
Stabilization Units LNG Plant

Natural Gas Liquids Nitrogen

Dehydration
Recovery Rejection
Water Nitrogen

Helium Outlet Gas Gas to

Recovery Compression Pipeline
Helium
C2
Field Operation Natural Gas Liquids Sweetening C3
Gas Processing Plant Operation Fractionation Units C4s
Not Available in all Gas Processing Plants C5+
Receive from Different Gas Processing Plants

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Natural Gas Processing and Liquefaction

Dehydration
Introduction
The major reasons for removing the water from natural gas are as follow:

1) Natural gas in the right conditions can combine with liquid or free water to form solid
hydrates that can plug valves fittings or even pipelines.
2) Water can condense in the pipeline, causing slug flow and possible erosion and
corrosion.
3) Water vapor increases the volume and decreases the heating value of the gas.
4) Pipeline specifications often have to meet a maximum water content (usually 4-7 lb
H2O/MMscf (60 to110 mg/Sm3))
5) If C2+ fraction is to be recovered (usually needs cryogenic conditions), removal of water
down to 0.1 ppmv is required

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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination (1)
The first step in evaluating and/or designing a gas dehydration system is to determine the
water content of the gas.
In any mixture, where both the gas and liquid phases are in equilibrium, each component
in the mixture obeys the relationship

xi is the mole fraction in the liquid phase

Ɣi is the activity coefficient, f (T, P, composition)
Psat is the saturation or vapor pressure, f(T)
yi is the vapor phase mole fraction,
φi is the vapor phase fugacity coefficient, f (T, P, composition)
P is the total pressure

The activity and fugacity coefficients can be calculated by use of equations of state and/or
empirical equations. However, present-day equations of state have difficulty modeling the
strong polar nature of water in hydrocarbon−water mixtures; calculations from different
simulators can give different results, especially in prediction of water content in the liquid
phase.
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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination (2)
A reasonably good estimates of the concentration of water in the vapor phase in
equilibrium with liquid water can be made at pressures below 500 psia (35 bar). If we make
the good assumption of negligible hydrocarbon in the liquid water phase, which, thus
makes both xi and Ɣi unity for water and assume the gas phase to be ideal, which makes φi
unity, we obtain

Equation above provides reasonably good values for gas-phase water content, provided
that the gas contains low mol% of CO2 or/and H2S (total less than 3%) and the above
assumptions are valid

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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method
A more accurate method is to use Wickert method. It is chart based method that provides
good estimates of the equilibrium water vapor content of sour natural gas for a range of
conditions, including acid gas concentration up to 40 mole%, pressures up to 10,000 psia,
and temperatures from 50 to 347◦F. The overall average error of this method is less than
1%. However, sometimes shows discrepancy up to about ±10%.

1) Determine the equilibrium water vapor content of sweet gas at the operating
temperature and pressure conditions using Figure A.
2) Determine the mole % H2S equivalent concentration of the sour gas as
mole % H2S equivalent = mole % H2S + 0.7 × mole % CO2
If the mole% H2S equivalent is less than 5%, the number you obtained is the
equilibrium water vapor content. Otherwise, proceed to next steps.
3) From Figure B at the bottom left-hand temperature scale, move to the right to the
mole % H2S equivalent (interpolate between the lines if necessary)
4) From this point, move to the upper chart, to the pressure of interest. From the
pressure point, move to the left, to the ratio scale.
5) Multiply the value from step 4 by the water content determined for sweet gas in
step 1. The result is the estimate of the saturated water content of the sour gas at
the pressure and temperature of interest.
Dr. Tamer Samir © 178

Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method – Figure A

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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method – Figure B

Dr. Tamer Samir © 180

Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method – Example (1)
Calculate the water content of the sour natural gas shown in Table below by use of both
methods you learned so far at the following conditions:
a) 300 psia and 80°F
b) 1,000 psia and 80°F

Component Mole Fraction

CH4 0.83
C2H6 0.04
C3H8 0.03
n-C4 0.02
N2 0.01
CO2 0.03
H2S 0.04

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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method – Example (2)
1st Method:

1 Ibmol=453.6 gmol
PV=nRT
At 1 atm and 60 oF (15.6 oC),
At 80°F, PsatH20= 0.507 psia
V=453.6*0.082*(15.6+273.15)/1=10740 lit
yH2O (300 psia) = 0.507/300 = 0.0017 =379.3 scf
yH2O (1000 psia) = 0.507/1000 = 0.000507
Convert the mole fraction to Ib/MMscf so that we can compare with the 2nd method

 mol H 2O   Ib H 2O   1Ibmol  6
WH 2 0  300 psia    0.0017  18   
 10  80.6
Ib H 2O
 mol gas   Ibmol H 2O   379.3 scf  MMscf
 mol H 2O   Ib H 2O   1Ibmol  6
WH 2 0 1000 psia    0.000507  18   
 10  24
Ib H 2O
 mol gas   Ibmol H 2O   379.3 scf  MMscf

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Natural Gas Processing and Liquefaction

Dehydration
Water Content Determination – Wickert Method – Example (3)

2nd Method :
-Mwt = ∑yi Mwti = 19.92
- SpGr =Mwt-Gas/Mwt-air = 19.92/28.96 = 0.688
-From Figure A:
-water content of sweet gas without corrections (300 psia, 80°F) = 85 Ib H2O/MMscf
-water content of sweet gas without corrections (1000 psia, 80°F) = 37 Ib H2O/MMscf
-First correction (CG) at Mwt = 19.92 or (spGr = 0.688) = 0.99
-Second Correction (CS) at 0% = 1
-water content of sweet gas with corrections (300 psia, 80°F) = 85*0.99= 84.2 Ib H2O/MMscf
-water content of sweet gas with corrections (1000 psia, 80°F) = 37*0.99=36.6 Ib H2O/MMscf
-mole % H2S equivalent = mole % H2S + 0.7 × mole % CO2=4+0.7* 3= 6.1 mol%
-From Figure B, Ratio (300 psia) =1.03 Error between the 2 methods
At 300 psia = 7%
- From Figure B, Ratio (1000 psia) =1.06
At 1000 psia = 38%
-Final water content (300 psia)= 84*1.03=86.7 Ib H2O/MMscf
Dr. Tamer Samir © 183
-Final water content (1000 psia)= 36.6*1.06=38.8 Ib H2O/MMscf

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