A PRELIMINARY PROJECT REPORT ON

Design of Claus Unit for Sulphur recovery

SUBMITTED TO THE SAVITRIBAI PHULE PUNE UNIVERSITY, PUNE IN

THE PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE AWARD OF THE DEGREE
OF

BACHELOR OF PETROCHEMICAL ENGINEERING

SUBMITTED BY

Aravind Menon Exam No: B150027128

Shivam Saroday Exam No: B150027137
Omkar Shinde Exam No: B150027139

DEPARTMENT OF PETROCHEMICAL ENGINEERING

MIT,Pune
SAVITRIBAI PHULE PUNE UNIVERSITY
2018-2019
 CERTIFICATE
This is to certify that the project report entitles

Design of Claus Unit for Sulphur recovery

Submitted by

Aravind Menon Exam No: B150027128

Shivam Saroday Exam No: B150027137
Omkar Shinde Exam No: B150027139

is a bonafide student of this institute and the work has been carried out by him/her
under the supervision of Dr. RR Joshi and it is approved for the partial fulfillment
of the requirement of Savitribai Phule Pune University, for the award of the degree
of Bachelor of Engineering (Petrochemical Engineering).

Dr. RR Joshi Mr. Datta B. Dandge

Internal Guide Head of Dept.
Dept. of Petrochemical Engg. Dept. of Petrochemical Engg.
Dr.Mr. Lalitkumar K. Kshirsagar
Principal
MIT,Pune 41

Place: Pune
Date :
 Design of Claus Unit for Sulphur recovery

Acknowledgments

This has been the light of the day due to invaluable contribution of certain individu-
als whose constant guidance, support and encouragement resulted in the realization
of our project.

We are thankful to our Guide Dr. RR Joshi and HOD of Petrochemical Engineer-
ing, Mr. Datta B. Dandge for providing us the necessary help and encouragement
whenever we needed, which has resulted in the success of our project.

We take this opportunity to thank Dr.Mr. Lalitkumar K. Kshirsagar, Principal of

MIT, for providing a healthy environment in the college, which helped us in concen-
trating on our task.

We would also like to thank all the staff members of our department, without whose
constructive suggestions and valuable advice, the simple idea, which had borne by
us, would not have been able to blossom forth to give such a beautiful bloom.

Last but not the least, we are grateful to all our friends and our parents for their
direct or indirect constant moral support throughout the course of this project.

Aravind Menon
Shivam Saroday
Omkar Shinde
(B.E. Petrochemical Engg.)

MIT, Department of Petrochemical Engineering I

 Design of Claus Unit for Sulphur recovery

Abstract

This project has been undertaken with the aim of designing a Sulfur Recovery
Unit (SRU). There are many processes for the recovery of sulfur from natural gas
but we have selected the Claus process, because the design of the process is eco-
nomically most favorable. The economics of the plant also make balance with the
efficiency and is most suited to wells of oil and gas most commonly encountered.The
unit selected for this purpose is designed to produce 80 tons of elemental sulfur per
day. This report includes the details of the Claus process, material and energy bal-
ances across the sulfur recovery unit (SRU) as a preleminary report.
Also in this work, the most important influencing parameters regarding the selection
of the proper catalysts for Claus SRU converters have been technically evaluated.
It is shown that the pore size and pore size distribution, size, shape, bulk density,
mechanical strength and attrition resistance of the catalyst particles are the main pa-
rameters which should be considered in selection of Claus catalysts. The general
classification of Claus catalysts and the most important specifications required for
proper selection of converter catalysts are also presented.
In summary, the focus on the future improvements in the Claus process makes this
project distinctive and particularly relevant for educating present or perspective en-
gineers.
Keywords— Claus Unit, Sulphur Recovery, Claus Catalyst

MIT, Department of Petrochemical Engineering II

 INDEX

1 INTRODUCTION 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Reasons for removing CO2 and H2S . . . . . . . . . . . . . . . . . . . . . 2
1.3 Importance of Sulphur . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.1 Commercial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.2 Biological role . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Economic Role . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4.1 Indian scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4.2 World scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5 Sulfur Recovery Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2 The Claus Process 10

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Claus Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.1 Classification of Claus catalysts . . . . . . . . . . . . . . . . . . . 14
2.3.2 General criterions for selecting a Claus catalyst . . . . . . . . . . . 16
2.4 Process Improvements . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

3 MATERIAL BALANCE 18
3.1 Overall Material Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4 ENERGY BALANCE 22
4.1 Overall Energy Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
 Design of Claus Unit for Sulphur recovery

5 Conclusion 26
5.1 Conclusion of preleminary report . . . . . . . . . . . . . . . . . . . . . . . 27
5.2 Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

6 References 28

MIT, Department of Petrochemical Engineering IV

List of Figures

1.1 Properties of Sulphur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.2 Sulphur consumption by industry . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Sulphur Production by states . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4 Sulphur Demand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

2.1 Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2.2 Claus Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3.1 Material Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

3.2 Material Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3 Stream composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

4.1 Energy Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

4.2 SRU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.3 Overall Energy Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
CHAPTER 1

INTRODUCTION
 Design of Claus Unit for Sulphur recovery

1.1 INTRODUCTION

Sulphur is a non-metallic element that occurs in both combined and free states and is dis-
tributed widely over the earth’s surface. It is tasteless, odorless, insoluble in water, and often
occurs in yellow crystals or masses. It is one of the most abundant elements found in a pure
crystalline form. The word sulphur is Latin for ”burning stone”, and was used almost in-
terchangeably with the term for fire. Because of its combustibility, sulphur was used for a
variety of purposes at least 4,000 years ago (Cunningham 1935). Although it is plentiful on
a world scale, native sulphur is usually found in relatively minute quantities. Deposits large
enough to warrant commercial exploitation are a rarity. The greatest quantity of naturally
occurring sulphur by far is combined with other elements, most notably the sulfides of cop-
per, iron, lead, and zinc, and the sulfates of barium, calcium (commonly known as gypsum),
magnesium, and sodium.
In the late 1800s the Frasch process - a mining technique that recovers from 75% to 92% of
a salt dome’s recoverable sulphur - became operational (Bodenlos 1973: 615). This made
the large underground sulphur deposits of the Texas and Louisiana salt domes exploitable,
and provided the world with a new source of high-purity (99.5%) elemental sulphur. These
stockpiles today (1992) account for more than 50% of the U.S. sulphur supply (see update
notes). By 1913 the United States had become the world leader in sulphur production; it
has never relinquished the lead (Whitehead 1931; Shelton 1979). Canada, Japan, France,
Poland, and Mexico are also major sulphur suppliers. Volcanic deposits are currently ex-
ploited in Indonesia and in Chile and other parts of South America.
Secondary sources of sulphur today are the sulphur dioxide (SO2) obtained from industrial
mineral, wastes, and flue gasses, and the hydrogen sulfide (H2S) found in ”sour” natural gas,
petroleum refinery products, and coke-oven gasses. Once considered unwelcome byprod-
ucts of industrial processes, these sources of sulphur have the advantage of being nearly
inexhaustible.

1.2 REASONS FOR REMOVING CO2 AND H2S

Carbon dioxide, hydrogen sulfide, and other contaminants are often found in natural gas
streams. CO2 when combined with water creates carbonic acid which is corrosive. CO2

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 Design of Claus Unit for Sulphur recovery

Figure 1.1: Properties of Sulphur

also reduces the BTU value of gas and in concentrations of more that 2 or 3 percent is un-
marketable. H2S is an extremely toxic gas that is also tremendously corrosive to equipment.
Amine sweetening processes remove these contaminants so that the gas is marketable and
suitable for transportation.The recovered Hydrogen Sulphide gas stream may be:

• Vented to atmosphere.

• Flared in waste gas flare or modern smokeless flares.

• Utilized for production for elemental Sulphur or Sulphuric acid.

• Incinerated for Sulphur removal.

1.3 IMPORTANCE OF SULPHUR

1.3.1 Commercial

Sulfur is used in the vulcanisation of black rubber, as a fungicide and in black gunpowder.
Most sulfur is, however, used in the production of sulfuric acid, which is perhaps the most
important chemical manufactured by western civilisations. The most important of sulfuric
acids many uses is in the manufacture of phosphoric acid, to make phosphates for fertilisers.

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 Design of Claus Unit for Sulphur recovery

Mercaptans are a family of organosulfur compounds. Some are added to natural gas sup-
plies because of their distinctive smell, so that gas leaks can be detected easily. Others are
used in silver polish, and in the production of pesticides and herbicides.

Sulfites are used to bleach paper and as preservatives for many foodstuffs. Many surfac-
tants and detergents are sulfate derivatives. Calcium sulfate (gypsum) is mined on the scale
of 100 million tonnes each year for use in cement and plaster.

1.3.2 Biological role

Sulfur is essential to all living things. It is taken up as sulfate from the soil (or seawater) by
plants and algae. It is used to make two of the essential amino acids needed to make proteins.
It is also needed in some co-enzymes. The average human contains 140 grams and takes in
about 1 gram a day, mainly in proteins.

Sulfur and sulfate are non-toxic. However, carbon disulfide, hydrogen sulfide and sulfur
dioxide are all toxic. Hydrogen sulfide is particularly dangerous and can cause death by res-
piratory paralysis.

Sulfur dioxide is produced when coal and unpurified oil are burned. Sulfur dioxide in the
atmosphere causes acid rain. This can cause lakes to die, partly by making toxic aluminium
salts soluble, so that they are taken up by living things.

1.4 ECONOMIC ROLE

1.4.1 Indian scenario

The production of sulphur recovered as by-product from fertilizer plants and oil refineries
were 561 thousand tonnes in 2016-17 as against 473 thousands tonnes in the preceding year.
The oil refineries in public sector reported production of sulphur. During the year 2016-
17, Indian Oil Corp. Ltd contributed about 84.60% of the total production during the year.
Among the states, Haryana accounted for 34.05% of the total sulphur production and it was

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 Design of Claus Unit for Sulphur recovery

Figure 1.2: Sulphur consumption by industry

followed by Gujarat 18%, Odisha 15.47%, Maharashtra 8.74%, Uttar Pradesh 8.31% , West
Bengal 6.88%, Kerala 5.94% and the remaining production was contributed by Assam and
Bihar. In addition, refineries of Hindustan Petroleum Corp. Ltd and RIL, Essar oil also
recover by-product sulphur which is in turn used as feedstock in manufacturing fertilizers
and pharmaceuticals. The Vadinar refinery of Essar Oil Ltd is also reported to produce by-
product sulphur. In Fertiliser Industry, the sulphuric acid is further used for manufacturing
phosphoric acid and single superphosphate (SSP) from rock phosphate.

India is deficient in sulphur and pyrites which are essential for fertilizer industry. Recovered
sulphur output was expected to increase significantly worldwide. Refineries in developing
countries were expected to improve environmental protection measures and eventually, com-
pare with the environmental standards of plants in Japan, North America and Western Europe

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 Design of Claus Unit for Sulphur recovery

in future. Higher sulphur recovery is likely to result from several factors, viz, higher refining
rates, higher sulphur content in crude oil, lower allowable sulphur content in finished fuels
and reduced sulphur emissions mandated by regulations.

1.4.2 World scenario

The world sulphur industry remained divided into two sectors, discretionary and non-discretionary
sector, the mining of sulphur or pyrites is the sole objective, this voluntary production of ei-
ther sulphur or pyrites (mostly naturally occurring iron sulphide) is based on the mining of
discrete deposits, with the objective of obtaining as nearly a complete recovery of the re-
source as economic conditions permit. Reserves of sulphur in crude oil, natural gas and
sulphide ores are large. As most sulphur production is a result of the processing of fossil
fuels, supplies should be adequate for the foreseeable future.

As petroleum and sulphide ores can be processed long distances from where they are pro-

Figure 1.3: Sulphur Production by states

duced, sulphur production may not be in the country for which the reserves were attributed.
For instance, sulphur reserves from Saudi Arabia may be recovered at oil refineries in the
United States or elsewhere in the world. In 2016, the world production of sulphur was es-
timated at 75.30 million tonnes and that of pyrites at 8 million tonnes in terms of sulphur
content as compared to 75.10 million tonnes 8.2 million tonnes respectively in the preceed-

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 Design of Claus Unit for Sulphur recovery

ing year. Elemental sulphur is obtained from ores by conventional mining or by the Frasch
method of mining or as a by-product of sour natural gas processing, sour crude refining, tar
sand processing and stack gas clean-up (recovered sulphur).

Elemental/native sulphur was mined in China, Poland and Russia. USA ranked 2nd in world
in sulphur production and in 2015 sulphur production in USA was about 9.3 million tonnes.
China was the leading producers of sulphur in all forms. Fertilizer production consumed
about two-third of the sulphuric acid produced in China.

World consumption of natural gas is expected to maintain strong growth, and sulphur re-
covery from that sector will likely to continue to increase. Natural gas continued to be the
fuel of choice in many regions of the world in the electric power and industrial sectors, in part
because of its lower carbon intensity compared with coal and oil, which makes it an attractive
fuel source in countries where governments are implementing policies to reduce greenhouse
gas emissions. Some of the future gas production is expected to come from unconventional
natural gas resources such as shale gas and coal bed methane. Use of unconventional gas
resources will certainly affect the sulphur supply outlook for the future as these gases have
low sulphur content.

However, increased sulphur from sour gas processing in China, central Asia is projected to
more than compensate for the decrease in sulphur resulting from unconventional natural gas
sources. Ore leaching will likely be the largest area of sulphur consumption growth. Copper
and nickel leaching are the major consumers of sulphuric acid. In the near term, increased
global production and continued demand will keep the sulphur market balanced, which is
expected to be followed in the long term by a surplus worldwide. International sulphur trade
is expected to increase significantly, driven by demand for sulphuric acid in industrial sectors
(particularly new ore-leaching operations) and a modest increase in demand for fertilizers.
World sulphur production decreased slightly however, it is likely to steadily increase for the
foreseeable future.

The largest increases in sulphur production during the next 5 years are expected to take
place in Iran, Kazakhstan, Qatar, Russia, Saudi Arabia, Turkmenistan and the United Arab
Emirates. New sulphur demand associated with phosphate/ fertilizer projects is expected

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 Design of Claus Unit for Sulphur recovery

in Algeria, Brazil, Egypt, Morocco and Saudi Arabia. According to TechSci Research re-
port, Global Sulphuric Acid Market, By Manufacturing Process, By Application, By Region
Competition Forecast and Opportunities, 2011 - 2025”, the global sulphuric acid market is
projected to register sales of $18 Billion in 2020, on account of surging demand for phos-
phate fertilizers such as DAP (diammonium phosphate), MAP (monoammonium phosphate),
TSP (triple superphosphate), SSP (single superphosphate), etc.

Global demand for phosphate fertilizers is projected to increase from 42.1 million tonnes
in 2015 to 45.6 million tonnes by 2019. Furthermore, global phosphoric acid production
is anticipated to increase from 46 million tonnes in 2015 to 51.9 million tonnes by 2019,
thereby augmenting consumption of sulphuric acid for production of phosphate fertilizers
in the coming years. Thus, expanding capacity to produce more phosphates, coupled with
growing application of sulphuric acid as a raw material for chemical manufacturing processes
and in metal leaching are further expected to drive global sulphuric acid market through
2025.

Figure 1.4: Sulphur Demand

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 Design of Claus Unit for Sulphur recovery

1.5 SULFUR RECOVERY METHODS

On a worldwide basis natural gas and crude oil are becoming sourer. As the sweeter, more
desirable natural gas and crude oil supplies are exhausted; more and more emphasis is placed
on these sour, less desirable feed stocks. The sulfur species in natural gas after its removal
is generally in the form of hydrogen sulfide (H2S). The most common means of recovering
the sulfur contained in hydrogen sulfide is the Claus process. This process can recover 93-99
percent of the sulfur contained in its feed. Recovery depends upon feed composition, age of
catalyst, and number of reactor stages. The gas leaving the Clause plant is referred to as tail
gas and is burnt to convert the remaining hydrogen sulfide, which is lethal at low levels, to
sulfur dioxide, which has a much higher toxic limit. The off-gas stream is vented to atmo-
sphere or sent to Tail Gas Recovery Plant.
Processes are differentiated on the bases of capacity as follows:

Medium (0.20 to 25.0 LTPD)

• Sulfa Treat DO (Direct Oxidation) is a medium scale process.

Large (greater than 25.0 LTPD)

• Clause process least expensive, well proven but only economical at large scales.

• Recycle Selectox Process.

• Selective Oxidation Process. - Parsons High Activity Process. - Super Clause Process.

• Wet Oxidation Based on Aqueous Solution. -Stratford and Sulfoline Process-SulFerox

Process. -Bio-SR Process.

• Cold Bed Absorption Process. - CBA 4 Reactor Scheme. - CBA 3 Reactor Scheme.

• Thermal Cracking of H2S.

MIT, Department of Petrochemical Engineering 9

 CHAPTER 2

THE CLAUS PROCESS

 Design of Claus Unit for Sulphur recovery

2.1 INTRODUCTION

The Claus process is the most significant gas desulfurizing process, recovering elemental
sulfur from gaseous hydrogen sulfide. First invented over 100 years ago, the Claus process
has become the industry standard. The Claus Process This is the least expensive, well proven
but only economical at large scales.

Figure 2.1: Flow Diagram

2.1.1 History

History The process was invented by Carl Friedrich Claus, a chemist working in England. A
British patent was issued to him in 1883. The process was later significantly modified by a
German company called I. G. Farbenindustrie A. G.

2.2 DESCRIPTION

The Claus technology can be divided into two process steps: thermal and catalytic.

Thermal Step

In the thermal step, hydrogen sulfide-laden gas reacts in a substoichiometric combustion at

temperatures above 850 C such that elemental sulfur precipitates in the downstream process

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 Design of Claus Unit for Sulphur recovery

Figure 2.2: Claus Process

gas cooler. The H2S content and the concentration of other combustible components (hydro-
carbons or ammonia) determine the location where the feed gas is burned. Claus gases (acid
gas) with no further combustible contents apart from H2S are burned in lances surrounding
a central muffle by the following chemical reaction:
H2S + 3/2 O2 → SO2 + H2O(H = -4147.20 kJ/kgmol)

Gases containing ammonia, such as the gas from the refinery’s sour water stripper (SWS),
or hydrocarbons are converted in the burner muffle. Sufficient air is injected into the muffle
for the complete combustion of all hydrocarbons and ammonia. The air to the acid gas ratio
is controlled such that in total 1/3 of all hydrogen sulfide (H2S) is converted to SO2. This
ensures a stoichiometric reaction for the Claus reaction.
The separation of the combustion processes ensures an accurate dosage of the required air
volume needed as a function of the feed gas composition. To reduce the process gas volume
or obtain higher combustion temperatures, the air requirement can also be covered by inject-
ing pure oxygen. Several technologies utilizing high-level and low level oxygen enrichment
are available in industry, which requires the use of a special burner in the reaction furnace
for this process option.
Usually, 60 to 70 perecent of the total amount of elemental sulfur produced in the process is
obtained in the thermal process step. The main portion of the hot gas from the combustion
chamber flows through the tube of the process gas cooler and is cooled down such that the
sulfur formed in the reaction step condenses. The heat given off by the process gas and the
condensation heat evolved are utilized to produce medium or low-pressure steam. The con-
densed sulfur is removed at the gas outlet section of the process gas cooler.
A small portion of the process gas can be routed through a bypass inside of the process gas

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 Design of Claus Unit for Sulphur recovery

cooler, as depicted in the here above mentioned figure. This hot bypass stream is added to
the cold process gas through a three-way valve to adjust the inlet temperature required for
the first reactor.

Catalytic Step
The Claus reaction continues in the catalytic step with activated aluminum (III) or titanium
(IV) oxide, and serves to boost the sulfur yield. The hydrogen sulfide (H2S) reacts with the
SO2 formed during combustion in the reaction furnace, and results in gaseous, elemental
sulfur. This is called the Claus reaction:
2 H2S + SO2 → 3/8 S8 + 2 H2O (H = -1165.60 kJ/kgmol)

The catalytic recovery of sulfur consists of three sub steps: heating, catalytic reaction and
cooling plus condensation.
These three steps are normally repeated a maximum of three times. Where an incineration
or tail-gas treatment unit (TGTU) is added downstream of the Claus plant, only two catalytic
stages are usually installed.
The first process step in the catalytic stage is the gas heating process. It is necessary to pre-
vent sulfur condensation in the catalyst bed, which can lead to catalyst fouling. The required
bed operating temperature in the individual catalytic stages is achieved by heating the pro-
cess gas in a reheater until the desired operating bed temperature is reached.
The typically recommended operating temperature of the first catalyst stage is 315 C to 330
C (bottom bed temperature). The high temperature in the first stage helps to hydrolyze COS
and CS2, which is formed in the furnace and would not otherwise be converted in the mod-
ified Claus process.The catalytic conversion is maximized at lower temperatures, but care
must be taken to ensure that each bed is operated above the dew point of sulfur. The operat-
ing temperatures of the subsequent catalytic stages are typically 240 C for the second stage
and 200 C for the third stage (bottom bed temperatures).

In the sulfur condenser, the process gas coming from the catalytic reactor is cooled to be-
tween 150 and 130 C. The condensation heat is used to generate steam at the shell side of
the condenser.

Before storage, liquid sulfur streams from the process gas cooler, the sulfur condensers and

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 Design of Claus Unit for Sulphur recovery

from the final sulfur separator are routed to the degassing unit, where the gases (primarily
H2S) dissolved in the sulfur is removed.

The tail gas from the Claus process still containing combustible components and sulfur com-
pounds (H2S, H2 and CO) is either burned in an incineration unit or further desulfurized in
a downstream tail gas treatment unit.
Inevitably a small amount of H2S remains in the tail gas. This residual quantity, together
with other trace sulfur compounds, is usually dealt with in a tail gas unit. The latter can give
overall sulfur recoveries of about 99.8 percent, which is very impressive indeed.

Gases containing ammonia, such as the gas from the refinery’s sour water stripper (SWS), or
hydrocarbons are converted in the burner muffle. Sufficient air is injected into the muffle for
the complete combustion of all hydrocarbons and ammonia. Air to the acid gas is controlled
such that in total 1/3 of all hydrogen sulfide (H2S) is converted to SO2. This ensures a stoi-
chiometric reaction for the Claus reaction.

2.3 CLAUS CATALYSTS

2.3.1 Classification of Claus catalysts

Two main types of catalysts are used in conventional Claus units: activated alumina (UOP
product numbers S-201 and S-2001) and titania catalysts (UOP product number S-7001).
They vary in their capability to hydrolyze COS and CS2 and to resist poisoning (sulfation).
These Claus catalysts may be used alone or in combination in the beds depending upon per-
formance requirements. The UOP S-201 catalyst delivers excellent results when H2S is the
primary compound to be removed from the feed gas. The new generation of activated alu-
mina Claus catalyst, S-2001, combines high macropore volume and BET surface area with
high physical strength and abrasion resistance. S-2001 is of special interest in sub-dewpoint
processes where higher macropore volume is especially important. S-2001 is also more ef-
fective for COS and CS2 conversion than S-201, and is therefore preferable for use in the first
reactor of a typical Claus plant. The UOP S-7001, a titanium dioxide-based Claus catalyst,
has a ailored pore structure that allows for high rates of diffusion of reactants and products.

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 Design of Claus Unit for Sulphur recovery

S-7001 is well suited for maximizing the conversion of COS and CS2 in the first converter.
In the second and third converters, it is very beneficial due to its resistance to sulfur poison-
ing and longevity in maintaining high H2S/SO2 conversion.
The general classification of Claus sulfur recovery catalysts together with the different man-
ufacturers are given below [5]:
1. Conventional alumina-based sulfur conversion catalyst used in natural gas plants, refiner-
ies and smelters having Claus process plants and other types of sulfur recovery plants: UOP,
S-201; Axens, CR; ShanDong XunDa, A918.
2. New generation catalyst for Claus units in natural gas processing plants, oil refineries,
coke plants, and sub-dewpoint tail gas units such as MCRC (Mineral and Chemical Resource
Co.), CBA (Cold Bed Adsorption) or Sulfreen. It provides high conversions of H2S/SO2,
COS and CS2 due to its high macroporosity, high surface area, and thermal stability: UOP,
S-2001; Axens, CR 3S; Almatis, DD431; ShanDong XunDa, A2000.
3. Sulfation resistant sulfur recovery catalyst used in natural gas plants, refineries, and
smelters having Claus process plants and other sulfur recovery plants. Also, used in first re-
actors for improved COS/CS2 conversion: UOP, S-501; Axens, CSM 31; ShanDong XunDa,
A931.
4. Promoted activated alumina that is used to scavenge oxygen in Claus reactors employing
alumina catalyst. It is used as a top layer in Claus catalyst beds to protect the alumina catalyst
bed beneath it from being poisoned by sulfation due to oxygen breakthrough: UOP, S-601;
Axens, AM; ShanDong XunDa, A958.
5. Specialty titania sulfur recovery catalyst for Claus units in natural gas processing plants,
oil refineries, and coke plants. It is particularly suited for use in the first converter for the
high conversion of COS and CS2. This extra high COS/CS2 conversion is especially impor-
tant for Claus plants that employ tail gas treating units that may not completely convert COS
and CS2, such as selective-oxidation units and sub-dewpoint systems: UOP, S-7001; Axens,
CRS 31; ShanDong XunDa, A988.
6. Top and bottom support in Claus catalyst beds and adsorption beds. The use of activated
alumina support allows for cost saving compared to the use of inert support due to the lower
bulk density of the activated alumina, and the activated alumina support provides some Claus
catalytic activity or adsorption capacity: UOP, CBS; Axens, DR.

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 Design of Claus Unit for Sulphur recovery

2.3.2 General criterions for selecting a Claus catalyst

There are various parameters which should be considered for final selection of a Claus cata-
lyst. Typical chemical and physical properties of a suitable alumina Claus catalyst are given
below[6]:

Composition Al2O3 > 93 wt%, Na2O:0.30.5 wt%, LOI (1000 8C):26 wt%
BET surface >325 m2/g
Particle size 1/8 to 1/4 in. (usually 3/16 in. 5 mm)
Particleshape : Firstconverter, 2nd and 3rd converters(spherical)
Meanporesize 40-90A
Total porevolume > 0.50mL/g
Macroporosity(> 750A) > 0.15mL/g
Mechanicalstrength(5mesh) > 140N/cm
Bulkdensity < 641kg/m3
Attritionloss < 0.4wt%

2.4 PROCESS IMPROVEMENTS

Over the years many improvements have been made to the Claus process. Recent develop-
ments include:

SUPERCLAUS (TM): A special catalyst in the last reactor oxidizes the H2S selectively to
sulfur, avoiding formation of SO2. Significantly higher conversions are obtained at modest
cost.

Oxygen Claus: The combustion air is mixed with pure oxygen. This reduces the amount of
nitrogen passing through the unit, making it possible to increase throughput.

Better Catalysts: Higher activities have been achieved with catalysts that provide higher
surface areas and macro porosity. More improvements can be expected.

CS2 destruction: Carbon disulfide (CS2) is a side product made in the furnace. Laboratory
work has shown that special catalysts operating in the furnace can destroy the CS2 before it
gets into the catalytic section. A commercially available catalyst like this might be developed

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 Design of Claus Unit for Sulphur recovery

for use in a Claus plant.

Catalyst Temperature Policy: The conversion of H2S goes faster at higher temperatures,
but a more favorable equilibrium is obtained at lower temperatures. It isn’t obvious whether
higher or lower temperatures are needed in the third converter. Kinetic modeling may supply
the answer, thereby improving conversion or reducing catalyst replacement cost.

MIT, Department of Petrochemical Engineering 17

 CHAPTER 3

MATERIAL BALANCE
 Design of Claus Unit for Sulphur recovery

3.1 OVERALL MATERIAL BALANCE

The material balance across the proposed sulfur recovery unit (SRU) is done by the conser-
vation equation of mass, as is done conventionally. A system must be defined to account
for the streams entering and leaving. In our case the obvious selection is the sulfur recovery
unit (SRU) itself, while all the other premises are considered surroundings. Some prelim-
inary bases are to be specified for the sake of convenience in the calculations. Following
specifications are taken to meet the above mentioned situation:

Sulfur production: 80 tons per day

Time of operation: 1 hr

Now the material balance calculations are made first along the whole unit and then across
individual equipments. It is to be noted that whether the calculations are made across the
whole unit or the individual equipments, the basic law of conservation of mass equation
remains the same and is given as:

Figure 3.1: Material Balance

The chemical reactions taking place are:

Main Reactions:
1- H2S + 3/2 O2 SO2 + H2O(eq 3.1)
2- SO2 + 2H2S 3/8 S8 + 2H2O(eq 3.2)
Side Reactions:

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 Design of Claus Unit for Sulphur recovery

Figure 3.2: Material Balance

3- CH4 + 2O2 CO2 + 2H2O(eq 3.3)
4- C2H6 + 7/2 O2 2CO2 + 2H2O(eq 3.5)
5- C3H8 + 5O2 3CO2 + 4H2O(eq 3.6)

Sulfur production target (S8)

= 80 ton/day
80 1 1000 1
tonnes day kg Kgmol
24 1 256.5
day hours tonne Kg

=13.0 kgmol/hr

H2S required by S8

= 16/3×13.0kgmol( f rom equ.3.3) = 69.30Kgmol

H2S supply for S8 (on account for 99.9% conversion from the Claus process)

= 0.999×69.30kgmol
= 69.37 kgmol

SO2 required by S8

=8/3×13.0kgmol( f romeq3.2)
= 34.65 kgmol

H2S consumed for SO2

= 34.65 kgmol (from equ. 3.2)

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 Design of Claus Unit for Sulphur recovery

Total H2S supplied

= 69.37 kgmol + 34.65 kgmol

= 104.03 kgmol

Total acid gas feed supply

= 104.03 kgmol /0.523

= 198.80 kgmol

Now the Stream-01 composition is as follows :

Figure 3.3: Stream composition

MIT, Department of Petrochemical Engineering 21

 CHAPTER 4

ENERGY BALANCE
 Design of Claus Unit for Sulphur recovery

4.1 OVERALL ENERGY BALANCE

The energy balance across the proposed sulfur recovery unit (SRU) is done by the conser-
vation equation of energy, as is done conventionally. A system must be defined to account
for the streams entering and leaving. In our case the obvious selection is the sulfur recovery
unit (SRU) itself while all the other premises are considered surroundings. Some prelim-
inary bases are to be specified for the sake of convenience in the calculations. Following
specifications are taken to meet the above mentioned situation:

Time of operation: 1 hr

Ambient temperature: 25o C

Ambient pressure: 1 atm

Now the energy balance calculations are made by using the following equation for the law
of conservation of energy:

Figure 4.1: Energy Balance

Furthermore, all the enthalpies of the streams are calculated by the following relation:
Q = (mCp) T

(4.2)

Where:
Q = amount of heat contained by the stream (kJ/hr)
m = molar flow rate of the stream (kgmol/hr)
Cp = Heat capacity of the stream (kJ/kgmolo C)
T= Temperature of the stream (o C)

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 Design of Claus Unit for Sulphur recovery

Figure 4.2: SRU

The chemical reactions taking place in the process are:

Main Reactions :
1- H2S + 3/2O2 → SO2 + H2O

(4.3) (H = -4147.20 kJ/kgmol)

2- SO2 + 2H2S →3/8S8 + 2H2O

(4.4) (H = -1165.60 kJ/kgmol)

Side Reactions:
3- CH4 + 2O2→ CO2 + 2H2O

(4.5) (H = -891.0 kJ/kgmol)

4- 4- C2H6 + 7/2O2→ 2CO2 + 2H2O

(4.6) (H = -1560.0 kJ/kgmol)

5- 5- C3H8 + 5O2→ 3CO2 + 4H2O

(4.7) (H = -2220.0 kJ/kgmol)

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 Design of Claus Unit for Sulphur recovery

Figure 4.3: Overall Energy Balance

MIT, Department of Petrochemical Engineering 25

CHAPTER 5

CONCLUSION
 Design of Claus Unit for Sulphur recovery

5.1 CONCLUSION OF PRELEMINARY REPORT

A vast majority (about 92%) of the 8 million metric tons of sulfur produced in the United
States in 2005 was recovered from industrial by-products using the Claus process [5] . How-
ever, the traditional Claus process does face limitations and various process improvements
have been investigated in order to satisfy the increasingly stringent emission regulations and
the need to process gas streams and fuels with higher sulfur content. New technologies have
to be developed in order to achieve 100% removal of sulfur compounds from industrial flue
gases.
The most important influencing parameters regarding the selection of a suitable catalyst for
Claus SRU converters are also introduced. It is shown that the best particle shape for 2nd and
3rd converters is spherical. The particle size should be in the range of 1/8 to 1/4 in. and the
BET surface needs to be greater than 325 m2/g. The total pore volume higher than 0.5 mL/g
and the macroporosity greater than 0.15 mL/g are required for proper operation of Claus
catalyst. Total surface area, particle shape and size, total pore volume and macroporosity are
the most determining factors for activity and durability of the Claus catalysts. The general
classification of Claus sulfur recovery catalysts together with the different manufacturers are
also presented in this report. These Claus catalysts may be used alone or in combination in
the beds depending upon performance requirements.

5.2 FUTURE WORK

• Adding to the existing overall material and energy balances, further more detailed
material and energy balances across each component used in the process will be pre-
sented.

• Also the design of individual equipments along with the costing will be carried out to
present the overall plant operational and fixed capital costs involved.

• Further investigations will be deliberated on improved and environmental friendly

catalysts with the aim of improving the overall efficiency of the proposed plant as
well as to reduce emmissions of So2 so as to reduce the overall environmental load of
the plant during operation.

MIT, Department of Petrochemical Engineering 27

CHAPTER 6

REFERENCES
 Design of Claus Unit for Sulphur recovery

[1] Indian Minerals Yearbook 2013 52nd edition(Part- III : Mineral Reviews) ,SULPHUR
AND PYRITES.

[2] ”Claus recycle with double combustion process” Ribhi El-Bishtawi, Noman Haimour*
University of Jordan, Amman 11942, Jordan Received 30 October 2003; accepted 25
April 2004

[3] ”Model-based optimization of sulfur recovery units ” Flavio Manenti, Davide Pa-
pasidero, Giulia Bozzano, Eliseo Ranzi Politecnico di Milano, Dipartimento di Chimica,
Materiali e Ingegneria Chimica G. Natta, Piazza Leonardo da Vinci 32, 20133 Milano,
Italy

[4] ”Plants Produce Valuable Energy Use it Wisely” Angie Slavens, Saba Khan Univer-
SUL Consulting Saqib Sajjad, Mohanakumaran Mani Abu Dhabi Gas Industries Ltd.
(GASCO)

[5] B. ZareNezhad, Technical Report, National Iranian Gas Company, Tehran, Iran, 2007.

[6] (a) R. Larraz, Hydrocarbon Process. 69 (1999); (b) S.W. Park, B.S. Choi, S.S. Kim, B.D.
Lee, J.W. Lee, J. Ind. Eng. Chem. 14 (2008) 166.

[7] V.F.C. Lins, E.M. Guimaraes, J. Loss Prev. Process Ind. 20 (2007) 91.

[8] ”Converting Hydrogen Sulfide by the Claus Process.”

http://www.nelliott.demon.co.uk/company/claus.ht ml

[9] Elsner, M.P., M. Menge, C. Mller and C.W. Agar, 2003. ”The Claus process: teaching
an old dog new tricks, Catalysis Today, 79-80: 487-94”

[10] Sulfur Production Report, 2006. United States Geological Survey http://en. wikipedia.
org/wiki/ Amineg ast reating

MIT, Department of Petrochemical Engineering 29