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Gas Treatment
Gas Treatment
id/staf/istadi )
Email: istadi@undip.ac.id
DEFINISI
Acid gas: gas alam yang mengandung H2S, dan CO2
Sour gas: gas alam yang mengandung H2S dan senyawa sulfur lainnya
(COS, CS2, dan mercaptan)
Sweet gas: gas alam yang mengandung CO2
Gas treating: reduction of the “acid gases” to sufficiently low levels to
meet contractual specifications or permit additional processing in
the plant without corrosion and plugging problems.
Questions:
Why are the acid gases a problem?
What are the acid gas concentrations in natural gas?
How much purification is needed?
What is done with the acid gases after separation from the natural gas?
What processes are available for acid gas removal?
Natural Gas Pipeline Specification
Acid Gas Definitions
Hydrogen Sulfida (H2S):
Hydrogen sulfide is highly toxic, and in the presence of water
it forms a weak corrosive acid.
threshold limit value (TLV): 10 ppmv
When H2S concentrations are well above the ppmv level,
other sulfur species can be present: carbon disulfide (CS2),
mercaptans (RSH), and sulfides (RSR), in addition to
elemental sulfur.
If CO2 is present, the gas may contain trace amounts of
carbonyl sulfide (COS).
ASTM D4084 Standard test method for analysis of hydrogen
sulfide in gaseous fuels
H2S…
At 0.13 ppm, H2S can be sensed by smell.
At 4.6 ppm, the smell is quite noticeable.
As the concentration increases beyond 200 ppm, the
sense of smell fatigues, and the gas can no longer be
detected by odor.
At 500 ppm, breathing problems are observed and
death can be expected in minutes.
At 1000 ppm, death occurs immediately.
Acid Gas Definitions
Carbon dioxida (CO2):
Carbon dioxide is nonflammable and, consequently, large
quantities are undesirable in a fuel.
it forms a weak, corrosive acid in the presence of water.
If the partial pressure of CO2 exceeds 15 psia, inhibitors
usually can only be used to prevent corrosion.
The partial pressure of CO2 depends on the mole fraction of
CO2 in the gas and the natural gas pressure.
Corrosion rates will also depend on temperature.
Threshold Limit Value (TLV): of a chemical substance is a
level to which it is believed a worker can be exposed day
after day for a working lifetime without adverse health
effects.
Gas Purification Level
The inlet conditions at a gas processing plant are
generally temperatures near ambient and pressures
in the range of 300 to 1,000 psi (20 to 70 bar), so
the partial pressures of the entering acid gases
can be quite high
If the gas is to be purified to a level suitable for
transportation in a pipeline and used as a residential
or industrial fuel, then the H2S concentration must
be reduced to 0.25 g/100 SCF (6 mg/m3)
the CO2 concentration must be reduced to a
maximum of 3 to 4 mol%
However, if the gas is to be processed for NGL
recovery or nitrogen rejection in a cryogenic
turboexpander process, CO2 may have to be
removed to prevent formation of solids.
If the gas is being fed to an LNG liquefaction facility,
then the maximum CO2 level is about 50 ppmv
Acid Gas Disposal
What becomes of the CO2 and H2S after their
separation from the natural gas? The answer
depends to a large extent on the quantity of the acid
gases. Warning: CO2 is the most greenhouse gas
contributor
For CO2, if the quantities are large sometimes used
as an injection fluid in EOR (enhanced oil recovery)
projects.
In the case of H2S, four disposal
options are available:
Incineration and venting, if environmental
regulations regarding sulfur dioxide emissions can be
satisfied
Reaction with H2S scavengers, such as iron sponge
Conversion to elemental sulfur by use of the Claus
or similar process (2 H2S + O2 → S2 + 2 H2O)
Disposal by injection into a suitable underground
formation, if concentration is too high
Acid Gas Removal Processes
Natural Gas Sweetening Processes
1. Batch solid bed absorption: For complete removal of H2S at
low concentrations, the following materials can be used: iron
sponge, molecular sieve, and zinc oxide.
2. Reactive solvents: MEA (monoethanol amine), DEA
(diethanol amine), DGA (diglycol amine), DIPA (di-isopropanol
amine), hot potassium carbonate, and mixed solvents. These
solutions are used to remove large amounts of H2S and CO2 and
the solvents are regenerated.
3. Physical solvents: Selexol, Recitisol, Purisol, and Fluor
solvent. They are mostly used to remove CO2 and are
regenerated.
4. Direct oxidation to sulfur. Stretford, Sulferox LOCAT, and
Claus. These processes eliminate H2S emissions.
5. Membranes. This is used for very high CO2 concentrations.
AVIR, Air Products, Cynara (Dow), DuPont, Grace, International
Permeation, and Monsanto are some of these processes
Process Selection? Please consider:
The type and concentration of impurities and hydrocarbon
composition of the sour gas.
The temperature and pressure at which the sour gas is available.
The specifications of the outlet gas (low outlet specifications favor the
amines).
The volume or flow rate of gas to be processed.
The specifications for the residue gas, the acid gas, and liquid products.
The selectivity required for the acid gas removal.
Feasibility of sulfur recovery
The capital, operating, and royalty costs for the process.
Acid gas selectivity required
Presence of heavy aromatic in the gas
Well location
Relative economics
The environmental constraints, including air pollution regulations and
disposal of byproducts considered hazardous chemicals.
PURIFICATION PROCESS
Four scenarios are possible for acid gas removal from
natural gas:
CO2 removal from a gas that contains no H2S
H2S removal from a gas that contains no CO2
Simultaneous removal of both CO2 and H2S
Selective removal of H2S from a gas that contains
both CO2 and H2S
Process selection chart for
CO2 removal with no H2S present
Process selection chart for
H2S removal with no CO2 present
Process selection chart for
simultaneous H2S and CO2 removal
Process selection chart for
selective H2S removal with CO2 present
CO2 and H2S Removal Processes for
Gas Streams
SOLVENT ABSORPTION PROCESSES
In solvent absorption, the two major cost factors are:
the solvent circulation rate, which affects both
equipment size and operating costs,
and the energy requirement for regenerating the
solvent
Comparison of Chemical and
Physical Solvents
Amine Structure
Primary amine
Secondary amine
Tertiary amine
amines…
The amines are used in water solutions in
concentrations ranging from approximately 10 to 65
wt% amines
All commonly used amines are alkanolamines, which
are amines with OH groups attached to the
hydrocarbon groups to reduce their volatility
Molecular structures of commonly used amines
Amines remove H2S and CO2 in a two
step process
The gas dissolves in the liquid (physical
absorption).
The dissolved gas, which is a weak acid, reacts with
the weakly basic amines.
Absorption from the gas phase is governed by the
partial pressure of the H2S and CO2 in the gas,
whereas the reactions in the liquid phase are
controlled by the reactivity of the dissolved
species
Basic Amine Chemistry
Amines are bases, and the important reaction in gas
processing is the ability of the amine to form salts with
the weak acids formed by H2S and CO2 in an aqueous
solution
The reaction between the amine and both H2S and
CO2 is highly exothermic
Direct proton transfer:
R1R2R3N + H2S ↔ R1R2R3NH+HS−
The reaction between the amine and the CO2 is more
complex because CO2 reacts via two different
mechanisms.
When dissolved in water, CO2 hydrolyzes to form
carbonic acid, which, in turn, slowly dissociates to
bicarbonate.
The bicarbonate then undertakes an acid−base
reaction with the amine to yield the overall reaction
A second CO2 reaction mechanism, requires the presence of a labile
(reactive) hydrogen in the molecular structure of the amine.
The CO2 reacts with one primary or secondary amine molecule to form
the carbamate intermediate, which in turn reacts with a second amine
molecule to form the amine salt
The rate of CO2 reaction via carbamate formation is much faster
than the CO2 hydrolysis reaction, but slower than the H2S
acid−base reaction.
These reactions are reversible and are forward in the absorber (at low
temperature) and backward in the stripper (at high temperature).
Monoethanolamine
Monoethanolamine (MEA) is the most basic of the
amines used in acid treating and thus the most
reactive for acid gas removal.
It has the advantage of a high solution capacity at
moderate concentrations, and it is generally used
for gas streams with moderate levels of CO2 and H2S
when complete removal of both impurities is required.
A slow production of “heat stable salts” form in all
alkanol amine solutions, primarily from reaction with
CO2.
Oxygen enhances the formation of the salts.
MEA Reactions
2(RNH2) + H2S ↔ (RNH3)2S
(RNH3)2S + H2S ↔ 2(RNH3)HS
2(RNH2) + CO2 ↔ RNHCOONH3R
Some Representative Operating
Parameters for Amine Systems
Some of the sulfur produced might cake in the bed and oxygen should
be introduced slowly to oxide this sulfur, Arnold and Stewart [2]:
S2 + 2O2 ↔ 2SO2
Iron sponge ….
Zinc Oxide
Zinc oxide can be used instead of iron oxide for the
removal of H2S, COS, CS2, and mercaptans.
However, this material is a better sorbent and the exit H2S
concentration can be as low as 1 ppm at a temperature of
about 300 oC.
The zinc oxide reacts with H2S to form water and zinc
sulfide:
ZnO + H2S ↔ ZnS + H2O
A major drawback of zinc oxide is that it is not possible to
regenerate it to zinc oxide on site, because active surface
diminishes appreciably by sintering.
Much of the mechanical strength of the solid bed is lost
due to fines formation, resulting in a high-pressure-drop
operation.
Molecular Sieve
Molecular sieves (MSs) are crystalline sodium alumino
silicates (Al/Si) and have very large surface areas and a
very narrow range of pore sizes.
They possess highly localized polar charges on their
surface that act as adsorption sites for polar materials
at even very low concentrations.
This is why the treated natural gas could have very low
H2S concentrations (4 ppm).
In order for a molecule to be adsorbed, it first must be
passed through a pore opening and then it is adsorbed
on an active site inside the pore.
There are four major zones in a sieve bed
Adsorption zone in a molecular sieve bed
Sweetening of natural gas by
molecular sieves
If it is desired to remove H2S, a MS of 5 A* is selected
If it is also desired to remove mercaptans, 13 X* is
selected.
In either case, selection made to minimize the
catalytic reaction:
H2S + CO2 ↔ COS + H2O
Olefins, aromatics, and glycols are strongly adsorbed,
which may poison the sieves.