RUNNING HEAD: Claus Unit 1

Designing of a Claus unit to convert hydrogen sulfide (H2S) into elemental sulfur
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Designing of a Claus unit to convert hydrogen sulfide (H2S) into elemental sulfur

Introduction:

Elemental sulfur is the tenth most abundant element by mass in universe and the

fifth most common element on Earth. Even though it is mostly found on Earth as sulfide and

sulfate minerals, sulfur can sometimes be found in its pure, native form. This form of sulfur is

very rare. Among the numerous commercial and biological uses of sulfur, the most important

is its presence in proteins and vitamins, which helps sustain life on Earth. The mechanical

strength of human nails, hair and skin is also due to disulfide bonds (S-S) present in keratin

protein. The chief commercial use of Sulfur is seen in the production of sulfuric acid, which

is vital for the production of fertilizers, oil refining and many other chemical processes. Other

uses of sulfur include but are not limited to vulcanization of rubber, bleaching paper,

preservation of dried fruits, manufacture of many surfactants and detergents and formation of

gypsum which is used for making cement and fertilizers.

Since sulfur is not present in the environment in its natural form, it was

traditionally extracted by frasch process from the salt-dome mines. In the salt dome mines,

sulfur is scattered between porous limestone found between barren insoluble layer of rocks.

In frasch process, four deep holes are drilled from the cap-rock to the bottom of limestone-

sulfur formation. Super-heated water at about 170 ℃ is injected down the outer-most pipe.

Hot compressed air is introduced in the inner-most pipe. The combination of steam and

compressed air melts the sulfur and makes it less dense. This helps to push the molten sulfur

to push outwards through the third pipe. (Britannica.com). The fourth pipe is used to bring

out the excess super-heated water and compressed air out of the holes. This method produces

99% pure, light yellow sulfur. It is not the widely used method to extract sulfur since the
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early 20th century since when it is obtained as a by-product of refining high-sulfur natural gas

and crude oil.

In this paper, we will focus on the recovery of elemental sulfur from hydrogen

sulfide, which is actually the by-product produced in the petroleum industry, by Claus

process. This process was first patented by the chemist Carl Friedrich Claus in 1883. Claus

uses a feed-stock of acidic gases. These acidic gases are sent to a proprietary burner system,

where they are burnt sub-stoichiometrically with air. The resulting mixture of hydrogen

sulfide and sulfur dioxide reacts to form elemental sulfur, which is then removed through

condensation. This process is much more economically beneficial as compared to the frasch

process and has the added benefit of removing an extremely dangerous and toxic hydrogen

sulfide gas from petrol and crude oil. Some of the questions that will be answered in this

research reported are listed below:

1. What are the steps used performed for the recovery of sulfur from H2S in Claus process?

2. What is the effect of Claus process on the ecosystem?

3. Are there any alternatives available for the Claus process?

Claus process is being used in the world since early 2000’s when the petroleum

industry became much more popular. Hydrogen sulfide, a by-product of petroleum industry,

is very toxic and can cause serious danger to human health as well as the environment. When

it was treated with oxygen, before safely releasing it in the atmosphere, it was found that

liquid sulfur was produced as by-product. Thus, this method replaced the Frasch method as it

was more economically viable.

Brief description of sulfur-recovery unit:

Recovery of elemental sulfur is a multi-stage catalytic oxidation process of

hydrogen sulfide as shown in the following overall reaction:

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2H2S + O2 → 2S + 2H2O

A condenser, a gas re-heater and a catalyst chamber is present in every catalytic stage (sulfur-

recovery engineering Inc.) as shown in the image below:

The burner chamber normally operates at temperatures ranging from 980 to 1540 ℃ and

pressure ranging higher than 70 kPa. This high temperature ensures that other compounds

such as benzene, toluene, ethyl benzene, and xylene are properly destructed and does not clog

the downstream Claus catalyst. Before entering a sulfur condenser, hot gas from the

combustion chamber is quenched in a waste heat boiler that generates high to medium

pressure steam. About 80 percent of the heat released could be recovered as useful energy.

The acidic H2S gas is oxidized by air and one-third of H2S is converted into sulfur dioxide.

The final products of this stage are sulfuric acid, water, and the unreacted hydrogen sulfide

gas. The resulting sulfur dioxide subsequently reacts with the remaining unreacted hydrogen

sulfide according to the following equation.

2H2S + SO2 → 3S + 2H2O

The elemental sulfur is collected in the condenser. The condensed phase is separated from the

gas stream by draining it into a container. An interesting property of liquid sulfur is its
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increase in viscosity with increase in temperature. This is due to polymerization of sulfur.

Hence, the temperature of the condensed sulfur should be closely monitored to avoid

polymerization and clogging of pipes. (Sassi, M., Gupta, A., 2008). The remaining sulfur

dioxide and hydrogen sulfide reacts in the second reaction chamber and then in the third

reaction chamber. The catalyst used for this reaction is either aluminium (III) or titanium

(IV). It serves to boost the yield of sulfur. it should be kept in mind that the condensed sulfur

should not come in contact with the catalyst as it renders the catalyst ineffective.

Effect of Claus process on the environment:

In the early years, the Claus process had a lot of negative impacts on the environment. The

tail gases were usually exhausted into the air without any treatment on them. With passing

time, as the need to reduce SO2 emissions received a greater emphasis due to increasing

danger of acid rain, Claus process was modified in a way that it does not create significant

environmental irreversible impacts. It is now considered a safe process to implement and

operate, keeping in mind all the required control measure. There is a proper management and

monitoring plans for the produced gas emissions. These gases are first reduced in quantity

and then reacted in such a way that they are not a danger to the environment before releasing

them in the environment. The various disposal and/or treatment methods used in Claus unit in

present era for the main types of waste are listed below:

Hazardous solid waste:

This type of waste includes activated alumina, activated titania, hydrogenation

catalyst, solid sulfur, rags, insulation material, chemical and oil drums, etc. This poses a

critical significant danger to the environment as it causes soil contamination as well as it is

responsible for the degradation of ambient air quality. (Sarawy, A., Raslan, W., tawfeek, M.,

2016). These equipment’s are decontaminated using the proper disinfectant or the
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decontamination technology before releasing to governorate hazardous waste disposal area.

Before disposing them, they were collected in labelled, sealed containers.

Uncontaminated solid waste:

This category of waste produced in a Claus unit includes scrap metals, demolition

waste not containing asbestos, old equipment, etc. (Sarawy, A., Raslan, W., tawfeek, M.,

2016). These materials are transferred through certified transporters for further recycling.

Some of these biodegradable materials are buried in special designated land-filling areas.

Hazardous liquid waste:

This type of waste includes two categories; 1) oily contaminated water, 2) liquid

sulfur. Oily contaminated water creates a critical significant danger for the environment. This

is because it causes soil contamination as it turns the ground water 8 times more hypersaline

than the sea water. (Sarawy, A., Raslan, W., tawfeek, M., 2016). Due to this hypersaline

nature, the ground water at the unit area is unfit for using for potable, agriculture or,

industrial purposes. Oily contaminated water also degrades the quality of the surface water

and also results in spoilage of sewage treatment works. Oil water separator is used as a

treatment method in Claus unit. It separates oil from the water and then the clean water is sent

to sewage treatment unit or road side water drainage. Liquid sulfur poses a medium

significant danger to the environment as it only causes soil contamination. In order to treat

liquid sulfur, it is first cooled and solidified. After it cools down, it is treated as a hazardous

solid waste as described above.

Alternative technologies for sulfur recovery

Microbiological alternatives to recover sulfur from hydrogen sulfide are being

investigated throughout the world as it is a much more cost-efficient process and does not

involve the expertise or the cost required for the maintenance of the Claus unit. (Jensen, A.,
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Webb, C., 1995). Microbiological processes operate at an ambient temperature and at

atmospheric pressure so there is no need for maintaining high temperatures and pressures.

Some of the biological processes for recovery of sulfur are described below in detail.

The green-sulfur bacteria Chlorobium limicola can be used to recover sulfur as a

possible alternative to Claus process. Immobilized cells of Chlorobium limicola in a

strontium alginate matrix were used for sulfur recovery. (Kim et al., 1990). The overall

equation for this reaction is as follows:

hv
2n H2S + nCO2 → 2n S + n (CH2O) + n H2O

The disadvantage in the use of photosynthetic bacteria on such a large scale lie in their

anaerobic nature and their requirement for radiant energy and hence extremely large

transparent surface area. (Jensen, A., Webb, C., 1995).

Biogas, Thiobacillus ferrooxidans, packed in a bed can prove to be an effective

alternative method of Claus process. The microorganisms are immobilized on a peat and air

is continually fed to it along with the acidic gas. It results in the oxidation of hydrogen sulfide

to sulfur. This reaction takes place according to the following equation:

H2S + 1/2 O2 → S + H2O

The first reaction of this process where the biogas reacts with hydrogen sulfide to form Fe +2

ions and sulfur is an irreversible, second-order reaction. This is the rate-controlling reaction

of the process. (Jensen, A., Webb, C., 1995). A distinct advantage of the process is that the

reaction of hydrogen sulfide with iron sulfate is so rapid and complete that there is no danger

of releasing toxic gases into the environment. The elemental sulfur formed from this process

can be recovered very easily and has the purity level of up to 99.98% which is slightly more

than that achieved by the Claus process.

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Conclusion:

Claus process is the most significant gas desulfurizing process and is

responsible for extracting most of the elemental sulfur that we use today. It is a process that is

in accordance to the rules and regulations in place for a safe and healthy environment. It also

produces a very pure form of sulfur, that 99% pure. The problem arises in the cost

management for this process. Even if it is much cheaper than the traditionally used frasch

process, it is still very expensive that the third-world countries are not able to afford it. It is a

high time that the world looks for another solution of sulfur recovery that is much more cost-

efficient. Using micro-biological process for this purpose is one of that way, which is

explained in this paper, that can be further explored. This process does not have any cost for

maintaining a high temperature and pressure, neither does it require any extra waste disposal

or treatment mechanisms. In order for this process to be used in high-scale, much more

research is required.

References
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Sass, M., Gupta, A. (2008). Sulfur recovery from acid gas using the claus process and high

temperature air combustion (HiTAC) technology. American Journal f Environmental

Sciences 4(5) 502-511

Jensen, A., Webb, C. treatment of H2S containing gases: A review of microbiological

alternatives. Department of Chemical Engineering, UMIST, Manchester, UK.

Sarawy, A., Raslan, W., tawfeek, M. (2016). Environmental Impact Assessmentfor sulfur

recovery unit in natural gas liquid plants. Internation journal of engineering and scientific

research. 7(1). 1036-1044.

Frasch sulfur recovery. Britannica.com. retrieved from:

http://www.britannica.com/technology/mining/Solution-mining

Liquid sulfide oxidation process for hydrogen sulfide removal. Retrieved from:

http://www.sciencdirect.com/topics/engineering/claus-plant
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