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LECTURE10:
CLOUS PROCESS
MEROX PROCESSES

CHEMICAL TECHNOLOGY (CH-206)

Dr. Vimal Kumar
Department of Chemical Engineering

CLAUS PROCESS
TheClaus processis used to convert gaseous
hydrogen sulfide (H2S) into elemental sulfur (S) in
the presence of a catalyst.
Generally, it is also referred as sulfur recovery unit
(SRU).
It is widely used to produce elemental sulfur from
H2S from:

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raw

natural gas,and
the by-product sour gases containing hydrogen sulfide
derived fromrefining petroleum crude oiland other
industrial facilities.

In 2010, the world wide production of by-product sulfur was 68 M metric tons,
majorly from petroleum refiningandnatural gas processing plants.

CLAUS PROCESS: HISTORY

Events

19th century

The sodium carbonate (Na2CO3) was produced by the

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Timeline

Leblanc process.
Carl Friedrich Claus, a chemist working in England,
recovered sulfur from the waste calcium sulfide
(CaS), using bog iron ore and later bauxite (a mineral
with a high alumina content) as a catalyst, a by
product of the Leblanc process.
1883

Claus was granted a British patent for the process.

1936

I.G. Farbenindustrie a (German conglomerate of

chemical companies) modified the Claus process by
introducing a thermal conversion operation followed by
catalytic conversion process, which is the concept used
in modern Claus sulfur recovery units.

CLAUS PROCESS: H2S SOURCES

Most of the H2S, used in Clous process, is
originates from absorption processes using
various solvents from the by-product gases of
petroleum refining, natural gas processing, tar
sands processing, coal gasification, smelters, coke
ovens, etc.

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Some

of the solvents used for H2S absorption

includeamine gas treating, Rectisol and Selexol, etc.

In petroleum refineries, the H2S is derived from

the steam distillation of wastewaters (sour water)
containing dissolved H2S.

CLAUS PROCESS: FEED GAS

COMPOSITION
Mol%

Wt%

From an amine process

Component

Mol%

Wt%

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Component

From a sour water stripper

H2S

82.1

80.8

H2S

26.7

40.2

CO2

11.9

15.1

CO2

2.6

5.1

NH3

nil

nil

NH3

39.4

29.7

H2O

4.0

2.1

H2O

31.3

25.0

HC

2.0

2.0

HC

nil

nil

Notes: H2S is hydrogen sulfide, CO2 is carbon dioxide, NH3 is ammonia,

H2O is water and HC is hydrocarbons.
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CLAUS PROCESS: PROCESS FLOW

DIAGRAM
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CLAUS PROCESS: PROCESS

DESCRIPTION

The feed gas is burned in a reaction furnace using sufficient

combustion air to burn only one-third of the H 2S it contains.

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The furnacetemperature and pressureis maintained at about 1000

OC and 1.5 bar gauge (barg).

At those conditions, the Claus reaction occurs thermally in the reaction

furnace (i.e., without requiring any catalyst).

About 70% of the H2S in the feed gas is thermally converted into
elemental sulfur in the reaction furnace.
The hot reaction product gas, containing gaseous sulfur, is used to
produce steam in a waste heat boiler (or boiler) which results in
cooling the gases.
The gas is then further cooled and condensed in a heat exchanger
while producing additional steam.
The condensed liquid sulfur is separated from the remaining
unreacted gas in the outlet end of the condenser and sent to product
storage.

CLAUS PROCESS: PROCESS

DESCRIPTION
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The separated gas is then reheated and enters

the first catalytic reactor maintained at an
average temperature of about 305 C, where
about 20% of the H2S in the feed gas is converted
into elemental sulfur.
The outlet product gas from the first reactor is
cooled in another condenser while also producing
steam.
The condensed liquid sulfur is separated from the
remaining unreacted gas in the outlet end of the
condenser and sent to product storage.

CLAUS PROCESS: PROCESS

DESCRIPTION

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The separated gas from the second condenser is sent to another

reheater and the sequence of gas reheat, catalytic reaction,
condensation and separation of liquid sulfur from unreacted gas
is repeated for the second and third reactors at successively
lower reactor temperatures.

About 5% and 3% of the H2S in the feed gas is thermally converted into
elemental sulfur in the second reactor and third reactors, respectively.

The remaining gas (or tail gas) separated from the last
condenser is either burned in an incinerator or further
desulfurized in a "tail gas treatment unit" (TGTU).
In a Claus sulfur recovery plant having three catalytic reactors,
an overall conversion of at least 98% can be achieved.
The latest modern designs can achieve up to 99.8% conversion of
H2S into product sulfur that is 99+% saleable "bright yellow
sulfur".

CLAUS PROCESS: REHEAT

METHODS
The various methods used for the reheating
required upstream of each catalytic reactor
include:

gas-fired heaters using fuel gas and designed

to operate at sub-stoichiometric conditions to prevent
any oxygen (O2) from getting into the reactors which
can damage the catalyst.
Gas-to-gas heat exchangers in which cooled gas from
a condenser exhanges heat with the hot gas from the
upstream reactor.
Steam-to gas heat exchangers in which the cooled gas
from a condenser is heated with high-pressure steam.

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Direct

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CLAUS PROCESS: OTHER DESIGN

FEATRUES
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Older Claus sulfur recovery units were designed using only two
catalytic reactors.
Such units will typically convert only about 97% of the H 2S in the feed
gas.
Because of stringent environmental regulatory requirements in the
United States as well as many other nations, many of those older units
have been upgraded to include three reactors.
The tail gas from those that have not been upgraded is very probably
desulfurized further in a tail gas treatment unit.
When the feed gas to a Claus unit includes ammonia and
hydrocarbons(such as in the overhead gas from a petroleum refinery
sour water stripper), special designs of the reaction furnace burner are
available to provide complete combustion of those feed gas components.
To obtain higher reaction furnace temperatures and/or reduce the gas
volume to be processed, pure oxygen may be used to enrich the reaction
furnace combustion air.

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CLAUS PROCESS: REACTION

MECHANISM

The H2S is converted into elemental sulfur in the

presence of one mole of SO2for each two moles of H2S:
2H2S + SO23S + 2H2O (1)

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To have the above reaction in the required ratio of

components, combustion of one-third of the H 2S in the
feed gas is the first step in the Claus process:
H2S + 1.5 O2SO2+ H2O (2)
The overall process reaction, combining reactions (1)
and (2), is:
2H2S + O22S + 2H2O

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CLAUS PROCESS: CATALYST

Each catalytic reactors contain a bed of porous aluminum
oxide (Al2O3) or alumina as a catalyst.

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Generally, the depth of the catalyst is varied from 90 to 120

cm.
The catalyst not only increases the rate of reaction of the Claus
reaction (eq. 1), but also hydrolyzes the carbonyl sulfide (COS)
and carbon disulfide (CS2), which is formed in the reaction
furnace:
COS + H20H2S + CO2 (4)

CS2+ 2H202H2S + CO2 (5)

The H2S formed as per the hydrolysis equations (4) and (5),
most of it occurs in the first reactor, is then converted into
elemental sulfur as per the Claus reaction (1).

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CLAUS PROCESS: CATALYST

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Titanium dioxide (TiO2), produced fromanatase,

is also used as a catalyst in the Claus reaction.
Titaniacatalysts are more resistant to thermal
aging as compared to the alumina catalysts and
have higher activity for the hydrolysis of COS and
CS2, which allows the first Claus reactor to
operate at lower temperatures as compared to
alumina catalysts.
However, they are significantly more expensive
than the alumina catalysts.

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15

MEROX (MERCAPTON OXIDATION)

PROCESS
Merox Extraction

Merox Sweetening

MEROX (MERCAPTON OXIDATION)

PROCESS
The UOP Merox process is an efficient and
economical catalytic process developed for the chemical
treatment of petroleum fractions to remove

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sulfur

present as mercaptans (Merox extraction) or

to directly convert mercaptan sulfur to less-objectionable
disulfides (Merox sweetening).

This process is used for liquid-phase treating of

liquefied petroleum gases (LPG), natural-gas liquids
(NGL), naphthas, gasolines, kerosenes, jet fuels, and
heating oils.
It also can be used to sweeten natural gas, refinery
gas, and synthetic gas in conjunction with conventional
pretreatment and post-treatment processes.

UOP Universal Oil Products

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MEROX PROCESS
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To improve odor on all stocks (extraction or sweetening or

both)
To reduce the mercaptan content to meet product
specifications requiring low mercaptan content (sweetening)
To reduce the sulfur content of LPG and light naphtha
products to meet specifications (extraction)
To improve lead susceptibility of light gasolines (extraction)
To improve the response of gasoline stocks to oxidation
inhibitors added to prevent gum formation during storage
(extraction and sweetening)
To reduce the sulfur content of coker or fluid catalytic
cracking (FCC) C3-C4 olefins to save on acid consumption in
alkylation operations using these materials as feedstocks or
to meet the low-sulfur requirements of sensitive catalysts
used in various chemical synthesis processes (extraction)

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MEROX PROCESS
The most common mercaptans (thiols) removed are:
Methanethiol Ethanethiol-

CH3SH [m-mercaptan]

C2H5SH [e- mercaptan]

1-Propanethiol 2-Propanethiol Butanethiol tert-Butyl

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C3H7SH [n-P mercaptan]

CH3CH(SH)CH3[2C3 mercaptan]

C4H9SH [n-butyl mercaptan]

mercaptan- C(CH3)3SH [t-butyl mercaptan]

Pentanethiol-

C5H11SH [pentyl mercaptan]

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MEROX PROCESS: PROCESS

DESCRIPTION
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The UOP Merox process accomplishes mercaptan extraction

and mercaptan conversion at normal refinery rundown
temperatures and pressures.
Depending on the application, extraction and sweetening can be
used either singly or in combination.
The process is based on the ability of an organometallic catalyst
to promote the oxidation of mercaptans to disulfides in an
alkaline environment by using air as the source of oxygen.
For light hydrocarbons, operating pressure is controlled slightly
above the bubble point to ensure liquid-phase operation.
For heavier stocks, operating pressure is normally set to keep
air dissolved in the reaction section.
Gases are usually treated at their prevailing system pressures.

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MEROX PROCESS: EXTRACTION

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Low-molecular-weight mercaptans are soluble in

caustic soda solution.
Therefore, for LPG, or light-gasoline fractions, the
Merox process can be used to extract mercaptans.
In the extraction unit, the sulfur reduction
attainable is directly related to the extractablemercaptan content of the fresh feed.
In mercaptan-extraction units, fresh feed is charged
to an extraction column, where mercaptans are
extracted by a counter-current caustic stream.
The treated product passes overhead to storage or
downstream processing.

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MEROX MERCAPTANEXTRACTION
UNIT

Oxidizer

Excess Air

Disulfide

Extractor

Rich Merox
Caustic

Air
Steam heater

H2S free
feed

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Extracted
product

Disulfide
separator

Merox-Caustic
Solution
Catalyst
Injection

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MEROX EXTRACTION
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The mercaptan-rich caustic solution containing Merox catalyst

flows from the bottom of the extraction column to the
regeneration section through a steam heater, which is used to
maintain a suitable temperature in the oxidizer.
Air is injected into this stream, and the mixture flows upward
through the oxidizer, where the caustic is regenerated by
converting mercaptans to disulfides.
The oxidizer effluent flows into the disulfide separator, where
spent air, disulfide oil, and the regenerated caustic solution are
separated.
Spent air is vented to a safe place, and disulfide oil is decanted
and sent to appropriate disposal (may be hydrotreating unit).
The regenerated-caustic stream is returned to the extraction
column.
A small amount of Merox catalyst is added periodically to
maintain the required activity.

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MEROX PROCESS: SWEETENING

processing with intermittent circulation of

caustic solution
Minimum-alkali fixed-bed (Minalk*) processing, which
uses small amounts of caustic solution injected
continuously
Caustic-Free Merox* treatment for gasoline and
kerosene
Liquid-liquid sweetening

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In sweetening units, the mercaptans are converted

directly to disulfides, which remain in the product;
the total sulfur content of the treated stock is not
reduced.
Merox sweetening can be accomplished in four ways:

Fixed-bed

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MEROX SWEETENING:
FIXED BED SWEETENING (CONVENTIONAL)
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Supported catalyst: activated charcoal impregnated with nondispersible Merox catalyst

MEROX SWEETENING:
FIXED BED SWEETENING (CONVENTIONAL)
Fixed-bed sweetening is normally employed for raw or
thermally cracked chargestocks having endpoints above
about 120C.

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The higher-molecular-weight and more branched mercaptan types

associated with these higher-endpoint feedstocks are only slightly
soluble in caustic solution and are more difficult to sweeten.
The use of a fixed-bed reactor facilitates the conversion of these
types of mercaptans to disulfides.

In fixed-bed sweetening unit a reactor contains a bed of

specially selected activated charcoal impregnated with
nondispersible Merox catalyst and wetted with caustic
solution.
Air is injected into the feed hydrocarbon steam ahead of the
reactor, and in passed through the catalyst bed, the
mercaptans in the feed are oxidized to disulfides.

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MEROX SWEETENING:
FIXED BED SWEETENING (CONVENTIONAL)
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The reactor is followed by a settler for separation of caustic and

treated hydrocarbon. The settler also serves as a caustic reservoir.
Separated caustic is circulated intermittently to keep the catalyst
bed wet.
The frequency of caustic circulation over the bed depends on the
difficulty of the feedstock being treated and the activity of the
catalyst.
The fixed-bed Merox sweetening is used in the production of jet
fuels and kerosenes.
As a result of the development of the Merox fixed-bed system, jet
fuels and kerosenes (also diesel and heating oils) can be
sweetened at costs that are incomparably lower than those of the
simplest hydrotreater.
However, because of other particular jet-fuel quality requirements,
some pretreatment and post-treatment are needed whenever any
chemical sweetening process is used.

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MEROX SWEETENING:
FIXED BED SWEETENING
(MINALK)
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MEROX SWEETENING:
FIXED BED SWEETENING
(MINALK)
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The UOP Merox Minalk is applied to feedstocks that are

relatively easy to sweeten, such as catalytically cracked
naphthas and light raw naphthas.
This sweetening design achieves the same high efficiency as
conventional fixed-bed sweetening but with less equipment
and lower capital and operating costs.
The process relies on a small, controlled, continuous
injection of an appropriately weak alkali solution rather
than the gross, intermittent alkali saturation of the
catalyst bed as in conventional fixed-bed Merox sweetening.
This small injection of alkali provides the needed alkalinity
so that mercaptans are oxidized to disulfides and do not
enter into peroxidation reaction, which would result if the
alkalinity were insufficient.

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MEROX SWEETENING:
CAUSTIC-FREE MEROX
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The Caustic-Free Merox process is used for sweetening gasoline

and kerosene.
The process uses the same basic principles of sweetening in
which the mercaptans are catalytically converted to disulfides,
which remain in the treated hydrocarbon product.
The Caustic-Free Merox catalyst system consists of
preimpregnated fixed-bed catalysts, Merox No. 21 catalyst for
gasoline and Merox No. 31 catalyst for kerosene, and a liquid
activator, Merox CF.
This system provides an active, selective, and stable sweetening
environment in the reactor.
The high activity allows the use of a weak base, ammonia, to
provide the needed reaction alkalinity.
No caustic (NaOH) is required, and fresh-caustic costs and the
costs for handling and disposing of spent caustic are thus
eliminated.

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MEROX SWEETENING:
CAUSTIC-FREE MEROX
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The actual design of the Caustic-Free Merox unit

depends on whether it is used on gasoline or kerosene.
The reactor section is similar to the fixed-bed systems,
conventional and Minalk, except for the substitution of a
different catalyst, the addition of facilities for
continuous injection of the Merox CF activator, and
replacement of the caustic injection facilities with
ammonia injection facilities, anhydrous or aqueous.
For kerosene or jet fuel production, the downstream
water-wash system is modified to improve efficiency and
to ensure that no ammonia remains in the finished
product.
Other post-treatment facilities for jet fuel production
remain unchanged.

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MEROX SWEETENING:
CAUSTIC-FREE MEROX (FOR
GASOLINE)
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MEROX SWEETENING:
CAUSTIC-FREE MEROX (FOR KEROSENE JET
FUEL)
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MEROX SWEETENING:
LIQUID-LIQUID SWEETENING
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The liquid-liquid sweetening version of the Merox process is not in use

nowadays as refiners has switched to the new units as they are having
more active fixed-bed systems.
Hydrocarbon feed, air, and aqueous caustic soda containing dispersed
Merox catalyst are simultaneously contacted in a mixing device, where
mercaptans are converted to disulfides.
Mixer effluent is directed to a settler, from which the treated hydrocarbon
stream is sent to storage or further processing.
Separated caustic solution from the settler is recirculated to the mixer.
A small amount of Merox catalyst is added periodically to maintain the
catalytic activity.
The liquid-liquid sweetening is applicable to raw light, thermally cracked
gasolines and to components having endpoints up to about 120C.
The mercaptan types associated with catalytically cracked naphthas are
easier to oxidize than those contained in light raw or thermal naphthas,
and therefore liquid-liquid sweetening has been successfully applied to
catalytically cracked gasolines having endpoints as high as 230C.

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MEROX SWEETENING:
LIQUID-LIQUID SWEETENING
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MEROX PROCESS APPLICATIONS

Merox type

Gas

Extraction

LPG

Extraction

Natural gas liquids

Extraction, extraction plus sweetening

Light naphtha

Extraction, liquid-liquid sweetening,

Minalk sweetening, caustic-free sweetening

Medium or heavy naphtha

Liquidliquid sweetening
Caustic-free sweetening

Full-boiling-range naphtha

Extraction plus sweetening, Minalk

sweetening, fixed-bed sweetening, causticfree sweetening

Kerosene or jet fuel

Fixed-bed sweetening
Caustic-free sweetening

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Hydrocarbon stream

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PROCESS CHEMISTRY

4RSH O 2

Merox catalyst

2RSSR

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In Merox process an organometallic catalyst is used to accelerate

the oxidation of mercaptans to disulfides at or near ambient
temperature and pressure.
Oxygen is supplied from the atmosphere.
The reaction proceeds only in an alkaline environment.
The basic overall reaction can be written:

2H 2 O

Alkalinity

where R is a hydrocarbon chain that may be straight, branched,

or cyclic and saturated or unsaturated.
Mercaptan oxidation, even though slow, reportedly occurs
whenever petroleum fractions containing mercaptans are
exposed to atmospheric oxygen.
The Merox catalyst speeds up this reaction, directs the products
to disulfides, and minimizes undesirable side reactions.

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PROCESS CHEMISTRY
MEROX EXTRACTION

In Merox extraction, in which mercaptans in the liquid or

gaseous feedstocks are highly soluble in the caustic soda
solution as solvent, the mercaptan oxidation is done outside
the extraction environment.
Therefore, a mercaptan-extraction step is followed by
oxidation of the extracted mercaptan as follows:

RSH

Oil phase

NaOH

Aquesous phase

4NaSR O 2 2H 2 O

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NaSR

Aquesous phase

Merox catalyst

H 2O

4NaOH

Aquesous phase

2RSSR

Oil phase (insoluble)

According to these treating steps, the treated product has

reduced sulfur content corresponding to the amount of
mercaptan extracted.

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PROCESS CHEMISTRY
MEROX SWEETENING

In the case of Merox sweetening, in which the types of mercaptans in the

feedstocks are difficult to extract, the sweetening process is performed in situ
in the presence of Merox catalyst and oxygen from the air in an alkaline
environment.

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The mercaptan first transfers to the aqueous alkaline phase and there
combines with the catalyst.
The simultaneous presence of oxygen causes this mercaptan-catalyst complex
to oxidize, yielding a disulfide molecule and water.
This reaction at the oil-aqueous interface is the basis for both liquid-liquid
and fixed-bed sweetening by the Merox process and can be written:

4RSH O 2
Oil phase

Merox catalyst

Alkalinity

2R' SR 2RSH O 2
Oil phase

2RSSR
Oil phase

Merox catalyst

Alkalinity

2H 2 O

2R' SSR 2H 2 O
Oil phase

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MEROX PROCESS FEATURES

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Low Operating Cost and Investment

Requirement
Ease of Operation
Proven Reliability
Minimal Chemical-Disposal Requirements
Proven Ability to Produce Specification Products
High-Efficiency Design
High-Activity Catalyst and Activators

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QUALITY SPECIFICATIONS FOR THE

MEROX PROCESS
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PROCESS STATUS AND OUTLOOK

percent LPG and gases

30 percent straight-run naphthas
30 percent FCC, thermal, and polymerization gasolines
15 percent kerosene, jet fuel, diesel, and heating oils

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The first Merox process unit was put on-stream

October 20, 1958.
In October 1993, the 1500 th Merox process unit was
commissioned.
Design capacities of these Merox units range from as
small as 40 BPSD for special application to as large as
140,000 BPSD and total more than 12 million BPSD.
The application of the operating Merox units is
distributed approximately as follows:

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MEROX PROCESS ECONOMICS

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CLAUS PROCESS: REFERENCES

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J.H. Gary and G.E. Handwerk(1984),Petroleum Refining Technology and

Economics, 2nd Edition, Marcel Dekker, ISBN 0-8247-7150-8.
Fundamental and Practical Aspects of the Claus Sulfur Recovery Process P.D.
Clark, N.I. Dowling and M. Huang, Alberta Sulfur Research Ltd., Calgary,
Alberta, Canada
The SuperClaus process

Sulfur production report by the United States Geological Survey

Gas Processors Suppliers Association(GPSA) (1987),Gas Processors Suppliers

Association Engineering Data Book, 10th Edition, Gas Processors Suppliers
Association. (See Volume II, Section 22)
The Role of Claus Catalyst in Sulfur Recovery Unit Performance Terry
McHugh, Ed Luinstra and Peter Clark,presented at Sulphur 98 conference in
Tucson, Arizona, November 1998.
Arthur Kohl and Richard Nielson (1997),Gas Purification, 5th Edition, Gulf
Professional Publishing, ISBN 0-88415-220-0.
Howard F. Rase (2000),Handbook of Commercial Catalysts:Heterogeneous
Catalysts, 1st Edition, CRC Press, pp. 240 - 242, ISBN 0-8493-9417-1.
British patent 5,958 (1883)

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