Acid Gas Treatment

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Absorption of acid gases by a solvent

2 Sulfur recovery units

3 Tail gas treatment units

2
 Acid gas treatment
 Acid gas?
 Acid gas is a gas mixture containing significant quantities
of hydrogen sulfide (H2S), carbon dioxide (CO2) or
similar acidic gases;

 Origins?
 Gases (Fuel Gas, LPG…) from various operations in a refinery
processing sour crudes contain hydrogen sulfide (H2S) and
occasionally carbonyl sulfide (COS);
 Some H2S in refinery gases is formed as a result of conversion of
sulfur compounds in processes such as hydrotreating, cracking,
and coking.
 Acid gas treatment
 Acid gas treatment
 In refinery installations, acid gas treatment essentially
comprises absorption of H2S by a solvent and its conversion
into elementary sulfur.
 Some specific applications, such as the purification of gases
from partial oxidation of residues, may require simultaneous
removal of H2S, CO2 and COS.
 Acid gases are generally combined to be treated in a single unit
 The aim is to be able to regenerate the solvent streams loaded
with acid gas from the different absorption sections in one
single unit.
 Acid gas treatment

Conversion

Typical block diagram of H2S removal facilities in a refinery

 Acid gas treatment
 Acid gas treatment
 The amine treating unit is designed to removed acid gases
(H2S/CO2) in rich amine which returning from amine absorbers;

 Generated amine called Lean amine is send back to amine

absorbers for continuous acid gas absorber;

 Sour gas is send to SRU for sulphur conversion or

combustion.
 Acid gas treatment
 Acid gas treatment
 Absorption of Acid Gases
 Chemical Solvents

 The acid gas treatment processes used in refineries consist

mainly of scrubbing with regenerable solvents.
 There are three families of solvents:
• Chemical,
• Physical,
• Mixed solvents.
 Absorption of Acid Gases
 Chemical Solvents
 These solvents react chemically with H2S and CO2 by equilibrium
reactions.
 Absorption reactions are promoted by high pressure and low
temperature.
 The solvent can then be regenerated by inverting these conditions.
 The most common chemical solvents are:
• Aqueous amine solutions such as N-methyldiethanolamine (MDEA).
• mono and diethanolamine (MEA and DEA) and diisopropanolamine
(DIPA);
• Solutions of hot potassium carbonate;
• Diglycolamine (DGA) in an aqueous solution (Fluor process) which
behaves like ethanolamines.
 Absorption of Acid Gases
 Chemical Solvents
Chemical solvents, especially amine solutions are the best suited to
the operating parameters in refinery treatment units

 Amine (chemical solvent) used to absorb the acid gases are:

• Mono-ethanolamine (MEA);
• Di-ethanolamine (DEA);
• Methyl-di-ethanolamine (MDEA);
• Diglycolamine (DGA).

 In general, the diethanolamine process has been the most widely

used for refinery gas treating.
 Absorption of Acid Gases
 Physical Solvents
 These solvents allow the absorption of the acid compounds
without any chemical reaction.
 The differences in H2S and CO2 physical solubilities give the
solvents a selective H2S absorption property, as H2S is more
soluble than CO2,
 Such solvents are usually applied to synthesis gas treatment but
seldom or never in the refinery
 Absorption of Acid Gases
 Mixed Solvents
 These solvents are mixtures of a physical and a chemical solvent.
 The most well known is "Sulfinol“ developed by Shell, a mixture of
sulfolane and an ethanolamine (MDEA or DlPA).
 The use of mixed solvents remains limited in refinery units.
 Absorption of Acid Gases
Simplifed flow scheme of a sour gas scrubbing unit in a refinery.
 Absorption of Acid Gases
 Amine properties
MEA DEA MDEA DIPA DGA
Formula C2H7NO C4H11NO2 C5H13NO2 C6H15NO2 C4H11NO2

Molar mass (kg/kmol) 61.09 105.14 119.17 133.19 105.14

Melting point 10.5 28 -23 42 -12.5
Boiling point (oC) 170.6 269.2 247.4 248.9 221.3
at 101.325 Pa
Viscosity (PaS), 0.0241 0.38 0.101 0.87 0.04
at 20oC at 30oC at 20oC at 30oC at 15.6oC
Specific gravity d2020 1.0179 1.0919 1.0418 0.989 1.0572

Heat value at 15.6oC 2544 2510 2238 2887 2389

(J/kg.s.K) (at 30oC)
Flash point (oC) 93.3 137.8 129.4 123.9 126.7

Solubility in water 20oC, completely 96.4 - 87 completely

%m
 Absorption of Acid Gases
 Amine properties
 MEA was the first amine to be implemented because it was easier to
manufacture. However, compared to secondary and tertiary amines, the
drawback is that it is more corrosive. This is why MEA concentration
is limited to 15-18% wt.
 MEA is more prone to form degradation products than secondary or
tertary amines, particularly in the presence of COS.
 MEA is much less applied in refineries nowadays.
 Many units initially designed for MEA have been converted to DEA or
MDEA.
 Absorption of Acid Gases
 Amine properties
 DEA is commonly present in refinery treatments.
 Less corrosive than MEA.
 it can be employed in concentrations of 22 - 35% wt in water and
does not form significant degradation products in the presence of
COS.
 Absorption of Acid Gases
 Amine properties
 MDEA allows amine solution concentrations as high as 50% wt
because of its lesser corrosivity.
 Due to its chenical structure MDEA exhibits an absorption selectivity
for H2S rather than CO2
 Its main advantage is to allow a lower solvent circulation rate thanks to
the higher concentration limit of the solution.
 This justified its introduction in refinery H2S removal units.
 Chemical Reactions
 Reactions with H2S and CO2
The absorption reactions of H2S and CO2 with amine solutions are
exothermic. They are similar for primary and secondary arnines and can
be written as follows for a secondary amine such as DEA:

H2S + R2NH  R2NH2+ + HS- + Q (1)

CO2 + 2R2NH  R2NCOO- + R2NH2+ + Q (2)
CO2 + H2O + R2NH  R2NH2+ + HCO3- + Q (3)

Reaction 1 is instantaneous, reaction 2 occurs at an intermediate rate

whereas reaction 3 takes place at a slow rate.
 Chemical Reactions
 Reactions with H2S and CO2
The direct reaction with CO2 is not possible with tertiary amines due to
structural reasons. The reactions are as follows:

H2S + R2R’N  R2R’NH+ + HS- + Q (4)

CO2 + H2O + R2R’N  R2R’NH+ + HCO3- + Q (5)

Since reaction 5 is kinetically slow, tertiary amines such as MDEA

allow H2S to be absorbed selectively in the presence of CO2, It is
enough to limit the contact time between the amine and the gas to be
treated for CO2 absorption to be only partial (kinetic limit)
 Chemical Reactions
 Reaction with COS
 While COS is generally not a problem in refinery fuel gases. It
may have to be removed from liquefied petroleum gases (LPG).
 COS reacts with amines after hydrolysis to H2S and CO2:

COS + H2O  H2S + CO2

 This equilibrium reaction has relatively slow kinetics. it is
thermodynamically limited by a high H2S or CO2 concentration
in the product to be treated.
 As a result, COS hydrolysis requires low H2S and CO2
concentrations and enough contact time to occur at a significant
rate.
Equilibrium Curves
Equilibrium Curves
 Process
Flow scheme of a refinery amine treatment
 Process

The flow scheme of a conventional refinery installation including:

 High pressure treatment of hydrogen-rich gas recycle from
hydrodesulfurization;
 Fuel gas treatment;
 Liquid LPG cut treatment.
 Process

In this flow scheme, the rich solvent regeneration unit is common to

all the absorption sections:
 The rich amine flash drum is used to mix the three solvent
streams before regeneration.
 The liquid LPG cut treatment presented is the simplest that can
be installed. It includes the H2S absorption section and a
coalescer designed to recover the entrained amine. In some
applications, a more sophisticated arrangement is required for
LPG treatment (water wash at the outlet, specific design for COS
removal).
 Process performance
 In gas processing
The treated gas residual H2S content depends on:
• the pressure and temperature at the top of the absorber;
• the quality of amine regeneration.
 At low pressure (5 to 10 bar), the residual H2S content that can
be achieved in the treated gas is around 100 to 250 ppm vol.
Meanwhile, high pressure operation (such as natural gas
processing) allows H2S specifications below 4 ppm vol.
 The residual CO2 content (which is not very significant for
refinery treatments) varies according to operating conditions:
from 50 ppm volume for severe high-pressure applications, to
1000 or even 5 000 ppm vol when no stringent specification
needs to be complied with
 Process performance
 In LPG cut processing
 The residual H2S content is some 10ppm wt. Note that these cuts
usually require a finishing treatment in order to meet commercial
specltications.
 The residual COS content is around 10 to 50 ppm wt depending
on the initial amount of COS in the feed and the processing
scheme arrangement
 CONTENTS

1 Acid gas treatment

2 Sulfur recovery units

3 Tail gas treatment units

28
 Sulfur Recovery units
 Objective
 The objective of sulfur recovery in the refinery is to convert the
hydrogen sulfide generated in solvent scrubbing into sulfur, a
storable, marketable and non polluting product.
 Sulfur is recovered in the refinery by one or more sulfur plants
implementing the Claus process which achieves recovery ratios
of 94 to 98%.
 When higher ratios are dictated by administrative standards, an
additional installation called tail gas treatment is added and
gives recovery ratios of 99 to 99.9%
 Sulfur Recovery units
 Objective
 Sulfur recovery process is used to convert all sulphur compounds
in the acid gas stream into elemental sulphur.

 The most practical method for converting hydrogen sulfide to

elemental sulfur is the modified Claus process.

 The modified Claus process best suited for acid gas containing
50% or more hydrogen sulfide is the partial combustion (‘‘once-
through’’) process.
 Sulfur Recovery units
 Typical Feeds
Feeds to the unit are usually:
 The main acid gas stream from absorption units, that contains
basically H2S (89 to 94%), water (about 5%) and carbon dioxide
(0 to 5%).
 It is available at low pressure (0.4 to 0.7 bar) and at a temperature
of 40 to 55°C.
 The effluent from the process water stripper, that contains
ammonia, H2S and water, generally at 80oC.
 Sulfur Recovery units
 Chemical Reactions
The reaction is in fact carried out in two stages:
 The thermal phase:
H2S + 3/2 O2  SO2 + H2O (2) Ho298 = -518kJ/mol

 The Claus reaction:

2H2S + SO2  2H2O + 3/n Sn (3) Ho298 = -41kJ/mol (S2 gaz)
Ho298 = -143kJ/mol (S8 liq)
The overall reaction is:
H2S + 3/2 O2  3 H2O + 3/n Sn (1) Ho248 = -186,6/221 kJ/mol
 Sulfur Recovery units
 Thermodynamic

H2S conversion effect of pressure and temperature

 Sulfur Recovery units
 Thermodynamic
 Sulfur Recovery units
 Thermodynamic
 Sulfur Recovery units
 Thermodynamic
 Sulfur Recovery units
 Thermodynamic
 Sulfur Recovery units
 Thermodynamic
 In industrial units, reaction (2) takes place in the combustion
chamber of a reaction furnace where 1/3 of the H2S is burned to
produce SO2.
 Reaction (3) begins with low conversion in this furnace where
the temperature is high and continues in the catalytic converters
that operate at lower temperature.
 Sulfur Recovery units
 Other Reactions
(4)
During the thermal
phase, impurities lead (5)
to the following side
reactions: (6)

(7)

(8)

(9)

(10)

(11)
 Sulfur Recovery units
 Other Reactions
 Reactions (4) to (6) are exothermic. They consume oxygen and
generate inert gases (H2O, CO2), thereby diluting the reaction
medium.
 The other reactions generate organic sulfur compounds, carbonyl
sulfide (COS) and carbon disulfide (CS2), which are not
converted by the Claus reaction, thereby reducing the final
conversion to sulfur.
 The dissociation of hydrogen sulfide (reaction 8) takes place in
conversion during the thermal stage due to the high temperature
(1300°C).
 Reactions (8) and (9) supply the reducing gases that will be
utilized in certain types of processes.
 Sulfur Recovery units
 Other Reactions
Claus reaction takes place on a solid catalyst. It is carried out in a
sequence of several stages with intermediate separation of the
resulting sulfur. Since the reaction is exothermic, conversion to
sulfur is promoted by low temperatures. However, a high enough
temperature must be maintained in order to:
 Promote Claus reaction kinetics;
 Prevent liquid sulfur condensation on the catalyst;
 Favor hydrolysis of organic sulfur compounds (COS and CS2
formed during the thermal stage of the process) by means of high
temperature.
COS + H2O  H2S + CO2
CS2 + 2H2O  2H2S + CO2
 Technology and Process
Typical flow scheme of a sulfur unit with two catalytic
stages.
 Technology and Process
Once-through Claus sulfur process
 Technology and Process

THERMAL STAGE CATALYTIC STAGE

H2S + 3/2 O2 → SO2 + H2O 2H2S + SO2 3S + 2H2O

(∆Ho298 = -518kJ/mol) (∆Ho298 = -41kJ/mol)
 Technology and Process
 A thermal
 A thermal section where one-third of the hydrogen sulfide contained in
the unit feed is burned with process air to produce a gas called "Claus
gas" which contains hydrogen sulfide and sulfur dioxide in the
stoichiometric molar ratio of two, which is the optimum for the Claus
reaction;
 Depending on the type and amount of impurities present, the
temperature varies from 950 to 1350oC and the residence time from 0.7
to 1.5 seconds.
 These two parameters are essential in reducing aluminum salt lay down
in the cold parts of the installation, and soot deposits and traces of
oxygen eventually sent to Claus catalysts.
 Technology and Process
 A condensation
A condensation section located immediately downstream from the thermal
section where the Claus gas is cooled in order to condense the produced
sulfur.
 A first catalytic stage
 A first catalytic stage that includes heating the Claus gas, catalytic
conversion as such, cooling and condensation of the sulfur.
 This stage implements the Claus reaction to produce sulfur but also
takes part in the hydrolysis of COS and CS2, which are undesirable
compounds formed upstream.
 This is made possible by operating the reactor at a temperature high
enough to promote hydrolysis at the expense of a lower sulfur
conversion at this stage.
 Technology and Process
 One or two further catalytic stages
 One or two further catalytic stages that include heating, conversion on
a catalyst and sulfur condensation.
 These stages complete the treatment that allows the Claus reaction to
perform at ever lower temperatures while maintaining sufficient
catalyst activity and preventing sulfur from condensing on the catalyst.
 The recovery yield in these units can vary from:
• 94 to 96% with two reactors,
• 95 to 97.5% with three,
• 97 to 98% with four.
 Technology and Process
 An incineration section
 An incineration section (either catalytic or thermal) where all the residual
sulfur compounds are converted into SO2 before being discharged into the
atmosphere.
 If specifications on residual H2S, COS, COS, CO and H2 content are stringent,
thermal incineration limits H2S to a few ppm (10 mg/std m3 usually) at around
600oC.
 An incinerator operating at 800°C is required to destroy completely all the
compounds mentioned above.
 At this temperature the heat can be recovered by heat exchange, between the
incinerator off gases and the tail gases entering the incinerator. It can also be
recovered by generating/superheating medium or high pressure steam.
 Catalytic incineration is possible too and generally operates between 300 and
500°C. However, the residual CO and COS content is higher than with
thermal incineration
 Technology and Process
 A degassing section
 A degassing section for the H2S in the liquid sulfur (approximately 250
ppm wt), since H2S can create serious risks during storage and
transportation due to its toxic and explosive nature.
 Sulfur degassing to 10 ppm of H2S can be achieved by various
processes, including the Aquisulf process from Elf Exploration
Production. Here degassing is performed by spraying recirculated
sulfur and injecting a small amount of catalyst.
 Technology and Process
 Impurities Removal in the Thermal Phase
Maximum Hydrocarbon Content
 The presence of hydrocarbons in the acid gas feed causes more air
to be consumed (6.5% for 1% more C2H6) and can lead to carbon
formation.
 This can foul the catalyst of the following stage and lower the
quality of the resulting sulfur. As a result, it is recommended to
limit the hydrocarbon content to 0.5-1%vol of methane equivalent.
 Technology and Process
 Impurities Removal in the Thermal Phase
Ammonia Destruction
 The presence of ammonia in sulfur units causes plugging (ammonium sulfides
and sulfites), catalyst sulfation and equipment corrosion.
 These problems occur with an ammonia content of a few tens of vpm. A few
hundred ppm of NH3 can usually be allowed in the feed of a burner operating
at a minimum of 1250oC. If the ammonia concentration is higher, three types of
configuration can be contemplated:
• If ammonia amounts to a few percent a high efficiency burner is used with
preheating of the acid gas and the air (Figure A);
• If the acid gas H2S content is low (15 to 30% H2S), a single burner is used
with a bypass for part of the feed so as to raise the temperature of the first
zone (Figure B);
• When the ammonia content is very high because of the input of water
stripper gases. a two burner system is used (Figure C).
 Technology and Process
 Impurities Removal in the Thermal Phase
Ammonia destruction.
A Acid gas and air preheating.
B. Combustion in a single burner (bypass).
C. Combustion with two burners
 Technology and Process
 Catalytic Conversion
 The aim is to continue H2S and SO2 conversion beyond the 65% figure
which is generally achieved at the exit of the thermal phase.
 The reaction must also enhance the hydrolysis of COS and CS2 in order
to do so it is necessary to:
• Shift the thermodynamic equilibrium by condensing the sulfur;
• Operate at a temperature lower than 300oC to approach
thermodynamic equilibrium;
• Use active catalysts to improve the kinetics of approaching
equilibrium.
 In actual practice the unit comprises a sequence of in-series reactors
working at decreasing temperatures. Each one is associated with a
sulfur condenser and a gas heating system to raise the gas to the
temperature of the next reactor.
 Technology and Process
Catalysts: Al2O3 or TiO2 activated
 Sulfur Recovery by Oxidation

 When a very small amount of sulfur is recovered. i.e. 2 to 30 t/y at the

most, recovery can be carried out by a direct oxidation process.
 This serves as a substitute for solvent scrubbing followed by a Claus
operation and its associated treatment of residual gases.
 Small amounts of sulfur can be found in:
• small capacity refineries (500 000 to 2 000 000 t/year) processing
low-sulfur crudes with a low-complexity flow scheme:
• lubricant production units;
• or possibly in synthesis gas production units of moderate capacity
using partial oxidation, where the low H2S sour gas can entail
costly scrubbing enrichment units.
 Modern technologies implement a redox process using iron chelates as
a substitute for the old Stretford vanadium process.
 Sulfur Recovery by Oxidation
Process flow of Superclaus
 Sulfur Recovery by Oxidation
Stretford Process
 Sulfur Recovery by Oxidation
Chelate Processes
These processes use Fe2+/Fe3+ as a redox pair

Conventional ARI LOCAT process.

 CONTENTS

1 Acid gas treatment

2 Sulfur recovery units

3 Tail gas treatment units

59
 Tail Gas Treatment Units

 Incinerating the residual hydrogen sulfide after recovering the

sulfur significantly increases the refinery's SO2 emissions. As a
result, further sulfur recovery from the sulfur plant tail gases
often becomes necessary.
 It is one of the first methods of reducing these SO2 emissions.
 Final sulfur recovery can reach 99 to 99.9% by implementing
supplementary units.
 At the outlet of the sulfur recovery unit, residual concentrations
of the various constituents vary according to the number and age
of catalytic reactors.
 Tail Gas Treatment Units
Composition of tail gases from a sulfur unit
 Tail Gas Treatment Units

Three main types of processes using different principles:

1. Claus reaction on solid or liquid catalysts.
2. H2S or SO2 recovery section with recycle to the Claus
unit, SO2 may not be recycled.
3. H2S oxidation reaction.
 Tail Gas Treatment Units
Claus reaction on solid or liquid catalysts.
 Tail Gas Treatment Units
H2S or SO2 recovery section with recycle to the Claus unit.
 Tail Gas Treatment Units
H2S oxidation reaction
 Tail Gas Treatment Units

Out of some 500 tail gas treatment units installed in the world,
over 2/3 use one of the following three processes:
 Sulfreen (Claus reaction on solid catalysts);
 Clauspol II (recent development of the Clauspol 1500)
with a liquid phase Claus reaction;
 SCOTand its derived processes (H2S recycle).
 Tail Gas Treatment Units
Sulfreen Process.
 Developed by Elf Aquitaine and Lurgi, the process has given rise to
several derived technologies (Amoco's CBA Delta Hudson's MeRe,
Davy McKee's Maxisulf).
 It operates at low temperature (below the sulfur dew point so that the
reaction equilibrium is shifted toward production of sulfur which
accumulates in the liquid form in the catalytic bed).
 It uses a Claus type catalyst in a fixed bed reactor.
 The principle of the Sulfreen process has been utilized by other
companies by combining the Claus reaction and adsorption (CBA
Process developed by Amoco, MeRe by Delta Hudson, Maxisulf by
Davy McKee).
 Tail Gas Treatment Units
Sulfreen Process.
 Tail Gas Treatment Units
Clauspol ll Process.
 First marketed by IFP uncer the name Clauspol 1500. the process was
then improved and called Claurpol II. It allows 99.8% of the sulfur to
be recovered over the whole process.
 It is based on the Claus reaction carried out in a solvent that absorbs
H2S and CO2 but is almost immiscible with liquid sulfur.
 The process results in a tail gas sulfur content of less than 300 ppm
expressed in sulfur.
 It also allows for great flexibillty with respect to variations in feed
characteristics (flow rate, H2S/SO2 ratio), due to the properties of the
solvent and of the dissolved catalyst which can absorb excess H2S and
CO2 at close to the stoichiometric ratio of 2.
 Tail Gas Treatment Units
Clauspol ll Process.
 Tail Gas Treatment Units
The SCOT Process (Shell Claus Offgas Treating)
 The process includes a section to reduce sulfur compounds (SO2, COS,
CS2 and elementary sulfur) to H2S on a cobalt-molybdenum catalyst.
 It operates at 300oC in the presence of hydrogen or of a hydrogen/CO
mixture. After cooling in two stages (steam generation then scrubbing
with water), the reactor effluent (3% H2S and up to 20% CO2) is
scrubbed counter-currently in a selective absorption column by
diisopropanol amine (DIPA) or MDEA.
 The treated gas, which contains only traces of H2S, is incinerated. The
concentrated H2S is stripped from the rich solvent, recovered at the top
of the regenerator and then recycled to the Claus unit.
 SCOT unit performance allows an overall recovery of 99.9% of the
potential sulfur present in the Claus unit feed (250 vpm in the off
gases).
 Tail Gas Treatment Units
The SCOT Process (Shell Claus Offgas Treating)
THANK YOU FOR YOUR
KIND ATTENTION

73