PMRE 413: Natural Gas Engineering

Sweetening Process

Shaumik Rahman Ayon

Lecturer
Department of Petroleum and Mineral Resources Engineering
Bangladesh University of Engineering and Technology (BUET)

Introduction

• Acid Gases: H2S , CO2 and other sulfur compounds.

• Natural gas containing H2S are classified as sour gas.
• Natural gas free of H2S is called sweet gas.

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Reasons for Removal of H2S

• H2S is deadly poisonous and corrosive to all metal normally associated with gas
transporting, processing and handling systems.
• On combustion H2S forms SO2 which is highly toxic and corrosive.
• H2S and other sulfur compounds can cause catalyst poisoning in refinery processes.
• H2S promotes hydrate formation
• It’s a contractual requirement from clients to reduce Sulfur content. Usually the
maximum allowable quantity is 4 ppm .

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Reasons for Removal of CO2

• CO2 has no heating value

• CO2 forms complex CO2.CO2 which is corrosive in presence of water.

• For gas being sent to cryogenic plants, removal of CO2 is necessary to prevent

solidification of CO2.

• CO2 promotes hydrate formation

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Classification of H2S Removal Process

• Non regenerative: Chemsweet process, NCA process, Slurrisweet process

• Regenerative process with recovery of H2S: Physical absorption process (water wash, selexol, fluor

solvent), amine process, hot carbonate process, molecular sieve process.

• Regenerative process with recovery of elemental S: Holmes stretford process, Giammarco-Vetrocoke

process

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Solid Bed Sweetening Processes

It is based upon physical or chemical adsorption of acid gases on the solid surface.
Examples:
1) Iron sponge process
2) Zinc oxide process
3) Molecular sieves process etc.

Advantage
• It offers simplicity, high selectivity and
process efficiency which is almost
pressure independent.
• It is best applied to gases with
moderate concentrations of H2S and
where CO2 is to be retained in the gas.
• It is relatively inexpensive.
Disadvantages
• Regeneration is difficult and expensive.
• High pressure loss through the bed.
• Inability to remove large amount of
sulfur.
• Does not produce saleable sulfur form:
difficulty in disposal.

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 Iron Sponge Process

The iron sponge process uses the chemical reaction of ferric oxide with H2S to sweeten gas
stream.
Reaction
Sour gas is passed through a bed of wood chips that have been impregnated with a special
hydrated form of ferric oxide that has high affinity for H2S.
2Fe2 O3 + 6H2 S → 2Fe2 S3 + 6H2 O
• Temperature should be at less than 120°F.
• The reaction requires the presence of slightly alkaline water and a pH level on the order of
8–10 should be maintained through the injection of caustic soda with the water.

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Iron Sponge Process

Regeneration
Batch process:
Iron oxide is regenerated by passing air over bed. The reaction with oxygen, is exothermic
and air must be introduced slowly so the heat of reaction can be dissipated.
2Fe2 S3 + 3O2 → 2Fe2 O3 + 6S
S2 + 2O2 → 2SO2
• Sulfur cakes over ferric oxide after several cycles reducing effective surface area.
• After 10 cycles, bed is removed and replaced.

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 Iron Sponge Process
Regeneration
Continuous Process:
• Small amount of air injected into sour gas feed.
• Requires higher pressure air stream
• Less effective than batch process.
• If not properly controlled, it may create explosive mixture of air and gas.

Upstream Gas Scrubber/Separator:

• Hydrocarbon liquids tend to coat the iron sponge media, inhibiting the reactions.
• Separator is added upstream at lower temperature or higher pressure so that
condensation does not take place at the iron sponge unit.

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Iron Sponge Process

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 Iron Sponge Process

Advantages Disadvantages
• Complete removal of small to medium • A batch process requiring duplicate installation
concentrations (300 ppm) of hydrogen sulfide or flow interruption of processed gas.
without removing carbon dioxide. • Prone to hydrate formation when operated at
• Relatively small investment, for small to higher pressures and at temperatures in the
moderate gas volumes, compared with other hydrate-forming range.
processes. • Effectually removes ethyl mercaptan that has
• Equally effective at any operating pressure been added for odorization.
• Used to remove mercaptans or convert them to • Coating of the iron sponge with entrained oil or
disulfides. distillate requires more frequent change out of
the sponge bed.

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Molecular Sieve Process

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Molecular Sieve Process
• The molecular sieve process uses synthetically manufactured solid crystalline
zeolite in a dry bed to remove gas impurities.
• It is porous in structure and has very large surface area.
• It adsorbs the molecules based on their size.
• The sieve posses highly localized charge on the surface area that acts as the
adsorption site for the polar material (Ex: H2S, water).
• It offers high H2S adsorption efficiency.
• Adsorption capacity increases with increasing H2S/CO2 ratio and decreases
with increasing temperature.
• Optimum operating pressure is about 450 psia.

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Molecular Sieve Process

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 Molecular Sieve Process

Regeneration
• Sieve bed is regenerated by flowing pre-heated (400-600oF) sweetened gas.
• Sour effluent is flared, 1-2% of gas treated is lost for regeneration.

Advantages Disadvantages
• Less susceptible to chemical degradation • High capital investment is required
• It offers a mean of simultaneous dehydration • Regeneration requires lot of heat
and desulfurization. • Physical damage by sudden pressure and
temperature change can reduce effectiveness.
• Limited to small gas streams at moderate
pressure.

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Molecular Sieve Process

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 Physical Absorption Processes
• These processes are based on the solubility of the H2S and/or CO2 within the
solvent, instead of on chemical reactions between the acid gas and the solvent.

• Solubility depends first and foremost on partial pressure and secondarily and
secondarily on temperature.

Examples:
1) Aquasorption Process
2) Flurol solvent process
3) Sulfinol process
4) Selexol process etc

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Physical Absorption Processes

Advantages Disadvantages
• Corrosion and fouling problem are minimal • Most solvents have relatively high solubility for
• Solvent used is recovered by flashing rich heavier HC particularly aromatics and
solvent in the flash tank at lower pressure unsaturated components. Hence danger of HC
• Low to no heat required for regeneration being lost with Sulphur.
• Offers good to fair selectivity. • Requires sulfur recovery unit since this
processes do not alter the acid components
chemically in any manner.

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Selexol Process

• This process uses dimethyl ether of polyethylene glycol (DMPEG) as a solvent.

H2S and CO2

CO2

Methane and CO2

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Chemical Absorption Processes

Chemical solvent processes use an aqueous solution of a weak base to chemically react
with and absorb the acid gases in the natural gas stream.

Examples:
1) Alkanol-Amine processes
2) Carbonate processes

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 Alkanol-Amine Processes

• Most prominent and widely used process for H2S and CO2 recovery.
• It offers good selectivity at low cost, good flexibility in design and operation.
• Solvents like MEA,DEA, TEA are normally used in this process.

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Alkanol-Amine Processes
Monoethanolamine (MEA) Diethanolamine (DEA)

• Highest reactivity. • Less corrosive

• Lower molecular rate thus highest removal capacity • Lower vapor pressure: Lower vaporization loss
on a unit weight/volume basis. • Requires less heat for regeneration.
• Chemically stable. • Slower reactions with carbonyl sulfide and carbon
disulfide, filtration problem is less.

• Nonselective for removal of H2S and CO2. • Less reactive than MEA.
• High vapor pressure: greater vaporization losses, puts • H2S removal to pipeline specs may cause problems.
limit to operating temperature. • Requires higher circulation rate.
• Irreversible reactions with carbonyl sulfide and carbon
disulfide.
• Efficient filtration is necessary as solids build up

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Alkanol-Amine Processes

Reflux
Condenser
Outlet
Scrubber

Cooler

HC
gas

Reboiler
Inlet
Scrubber Flash
Tank

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Elemental Sulfur Recovery

Direct conversion 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.

Example:
1) Claus process
2) LOCAT process etc.

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Claus Process
This process is used to treat gas streams containing high concentrations of H2S.

The chemistry of the units involves:

1. Partial oxidation of hydrogen sulfide to sulfur dioxide and

2. The catalytically promoted reaction of H2S and SO2 to produce elemental sulfur.

The reactions are staged and are as follows.

3
H2 S + O2 → SO2 + H2 O; thermal stage
2
SO2 + 2H2 S → 3S + 2H2 O; thermal and catalytic stage

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Claus Process

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Criteria for Process Selection

• The types and concentrations of impurities in the gas and the degree of removal
desired.
• Temperature and pressure at which the sour gas is available and at which sweet
gas is delivered.
• Volume of gas to be processed and HC composition.
• CO2 and H2S ratio in the gas.
• Economics of the process.
• The desirability of the S recovery due to environmental problems.

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Thank you!