Report on Sulphur recovery

Vishal Gaurav | B.E Chm with MBA(4th year) | CM16234

OBJECTIVE
1. Sulfur Recovery from Acid Gas Using the Claus Process and
High Temperature Air Combustion (HiTAC) Technology
2. Modeling and optimization of an industrial Claus process:
Thermal and catalytic section
3. Energy, exergy and sensitivity analyses of modified Claus
process in a gas refinery sulfur recovery unit
RESEARCH PAPER 1st
ABSTRACT
− Sulfur-bearing compounds are very detrimental to the environment and to
industrial process equipment. They are often obtained or formed as a by-product
of separation and thermal processing of fuels containing sulfur, such as coal, crude
oil and natural gas. The two sulfur compounds, which need special attention, are:
hydrogen sulfide (H2S) and sulfur dioxide (SO2). H2S is a highly corrosive gas with
a foul smell. SO2 is a toxic gas responsible for acid rain formation and equipment
corrosion. Various methods of reducing pollutants containing sulfur are described
in this paper, with a focus on the modified Claus process, enhanced by the use of
High Temperature Air Combustion (HiTAC) technology in the Claus furnace. The
Claus process has been known and used in the industry for over 100 years. It
involves thermal oxidation of hydrogen sulfide and its reaction with sulfur dioxide
to form sulfur and water vapor. This process is equilibrium-limited and usually
achieves efficiencies in the range of 94-97%, which have been regarded as
acceptable in the past years. Nowadays strict air pollution regulations regarding
hydrogen sulfide and sulfur dioxide emissions call for nearly 100% efficiency, which
can only be achieved with process modifications. High temperature air combustion
technology or otherwise called flameless (or colorless) combustion is proposed
here for application in Claus furnaces, especially those employing lean acid gas
streams, which cannot be burned without the use of auxiliary fuel or oxygen
enrichment under standard conditions. With the use of HiTAC it has been shown,
however, that fuel-lean, Low Calorific Value (LCV) fuels can be burned with very
uniform thermal fields without the need for fuel enrichment or oxygen addition.
The uniform temperature distribution favors clean and efficient burning with an
additional advantage of significant reduction of NOx, CO and hydrocarbon
emission.

Discussion
− Sulfur recovery from sour or acid gas typically involves application of the famous
Claus process[1] using the reaction between hydrogen sulfide and sulfur dioxide
(produced in the Claus process furnace from the combustion of H2S with air and/or
oxygen) yielding elemental sulfur and water vapor:

− 2H2S(g) + SO2(g) (3/n) Sn(g) + 2H2O(g) with Hr = −108 kJ moL

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 Therefore, higher conversions for this exothermic, equilibrium-limited reaction call
for low temperatures which lead to low reaction rates, imposing the use of a catalyst.
The catalytic conversion is usually carried out in a multi-stage fixed-bed adsorptive
reactors process, to counteract the severe equilibrium limitations at high conversions.
This technology process can possibly provide about 96-97% conversion of the influent
sulfur in H2S to S.

CONCLUSION
A review of the sulfur recovery process from acid gases has been presented. The
conventional modified Claus process and its derivatives have been presented and
discussed. It is shown that all improvements towards very high sulfur recovery induce
very high cost additions to an already economically deficient process. HiTAC has been
shown to feature great potential for an almost complete sulfur recovery from lean acid
gases.

The flameless or colorless combustion has been proposed to be a very promising

process for sulfur recovery and hydrogen production from rich acid gases. Therefore,
these last two technologies feature the potential for reducing the complexity and the
cost of the sulfur recovery process.

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RESEARCH PAPER 2ND
ABSTRACT
The main goal of this research is modeling and optimization of an industrial modified
Claus process to achieve maximum sulfur recovery. The modified Claus process consists
thermal conversion in furnace and catalytic conversion in two series fixed bed reactors.
The furnace and catalytic reactors are modeled based on the mass and energy
conservation laws at steady state condition. To prove the accuracy of the developed
mathematical model, simulation results of conventional process are compared with the
avail able plant data. Then, the optimal condition of Claus process is calculated
considering sulfur recovery as the objective function using Genetic algorithm as a useful
method in global optimization. The attainable decision variables are inlet temperature of
furnace and fixed bed reactors, feed distribution along the furnace and flow rate of air in
the furnace. The simulation results show that sulfur recovery is improved about 4.63% in
the optimized process compared to the conventional process. In addition, performance of
auto-thermal reactor as a substitute for conventional adiabatic reactors is investigated to
enhance sulfur recovery and reducing sulfur contaminants emission in the Claus process.

INTRODUCTION
Among all fossil fuels, natural gas has been used on a largescale due to relative
cleanliness, high thermal value and abundance for decades ;and the demand for this
energy source is also increasing in the future. Natural gas consumption rate is increasing
every year so that its annual demand growth rate for the last ten years and its
consumption in 2016 is equivalent to 2.3% and 3542.9 billion cubic meters respectively
(BP, 2017, June; Hafeznia et al., 2017). About 25 percent of natural gas coming from sources
and wells requires different sweetening process levels to participate in production
processes, therefore impurities should be eliminated. These processes are more important
in areas where natural gas hydrogen sulfide concentration is higher (Kazempour et al.,
2017; Mokhatab and Poe, 2012). One of the most suitable methods for hydrogensulfide
separation from the natural gas is converting to elemental sulfur. Elemental sulfur can be
easily stored in bulk. One of the major benefits of this product is the ease of storage that
allows sulfur to be stored economically at reduced demand times.

DISCUSSION
The sulfur recovery unit duty is to process the H2S-rich acid gas to produce liquid
elemental sulfur as well as prevent sour gas discharge in the atmosphere. The Claus

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process primary reaction was based on hydrogen sulfide oxidation with air (oxygen) in the
presence of a catalyst in a single-stage reactor. This reaction products were elemental
sulfur and water.

In order to better utilization of the generated heat by reaction (1) and increasing the
amount of sulfur recovery as well as increasing the capacity of sulfur recovery units, the
modified Claus process was presented so that the entire process is divided into two
thermal and catalytic sections. In the thermal section of the modified Claus process, some
of the hydrogen sulfide-rich acid gases are oxidized with the correct amount of
oxygen(from the air) and one-third of the hydrogen sulfide is converted to the sulfur
dioxide. Reaction (2) increases the process stream temperature greatly to encourage the
Claus reaction thermally. Then the hot gases are cooled in a waste heat boiler and are
routed into the catalytic reactors, where the catalytic reaction occurs according to
reaction(3).In this section ,to form the elemental sulfur,2molesof the hydrogen sulfide
reacts with 1 mole of sulfur dioxide (GPSA, 2004).

Due to the fact that a large amount of sulfur is formed in the furnace, and then is
separated from the gas stream in the condenser, the catalytic section load is reduced and
the unit conversionefficiencyisincreasedinthisprocess.Placingmorecatalytic steps following
the reaction furnace so that the condenser exhaust gases to be heated before routing into
the catalytic reactors, can result in increased conversion efficiency. In this case, the Claus
reaction is continued in the next catalytic stages with the difference that the remaining
H2S is combined with the SO2 in the next stages at far lower temperatures. Nowadays, the
Claus process is carried out based on the expressed method , however ,it may be changed
in the processes according to the unit conditions. This process produces very high-quality
sulfur and is considered as a source of a valuable chemical substance.

CONCLUSION

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In this study, the sulfur recovery unit based on the modified Claus process with the split
flow is simulated and the energy, exergy, exergoeconomic and sensitivity analyses are
performed on this unit. The results can be summarized as below:

1. The reaction furnace with an exergy destruction value of 4178kW has the highest
destruction rate and the reaction furnace is followed by K-104 boiler and P-7 pump so that
the percentage share of exergy destruction for the mis equivalent to 25.62%, 15.24%, and
12.07%, respectively. The lowest exergy destruction rate after mixers and separators is
related to CMPR4 and CMPR-5 compressors, and K-103 boiler, so that the share of each
equipment is about 0.02%. The highest capital investment and operating and maintenance
cost rates are related to the Hydrolyzing Claus bed ,WHBandP-7 pump with the values of
63.005 ($/h), 57.508 ($/h) and 47.627 ($/h), respectively.

2.Thelowestamountsoftheexergoeconomicfactorareassociated with the reaction furnace

and second condenser with the values of 0.26% and 0.86% respectively. According to the
results, the maximum values of the exergoeconomic facto rare related to the process
compressors with the values of about 94%.

3. The highest relative cost difference is related to the P-7 pump

withthevalueof807.5%andthelowestvaluesof this parameter after the mixers and separators
are associated to the second and third catalyst reactors with values of 0.437% and 0.513%
respectively.

RESEACH PAPER 3rd

ABSTRACT
The main goal of this research is modeling and optimization of an industrial modified
Claus process to achieve maximum sulfur recovery. The modified Claus process consists
thermal conversion in furnace and catalytic conversion in two series fixed bed reactors.
The furnace and catalytic reactors are modeled based on the mass and energy
conservation laws at steady state condition. To prove the accuracy of the developed
mathematical model, simulation results of conventional process are compared with the
available plant data. Then, the optimal condition of Claus process is calculated
considering sulfur recovery as the objective function using Genetic algorithm as a useful
method in global optimization. The attainable decision variables are inlet temperature of
furnace and fixed bed reactors, feed distribution along the furnace and flow rate of air in
the furnace. The simulation results show that sulfur recovery is improved about 4.63% in

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the optimized process compared to the conventional process. In addition, performance of
auto-thermal reactor as a substitute for conventional adiabatic reactors is investigated to
enhance sulfur recovery and reducing sulfur contaminants emission in the Claus process.

INTRODUCTION
Elemental sulfur is a bright yellow crystalline solid at room temperature. Under normal
conditions, sulfur atoms form cyclic oct atomic molecules with chemical formula S 8 . It is
a useful element that is used to manufacture of fertilizers with other principal users
including rubber industries, cosmetics, and pharmaceuticals. The modified Claus process
is the most popular method for recovery of elemental sulfur from hydrogen sulfide in oil
and natural gas re finery units. The modified Claus process is suitable when hydrogen
sulfide concentration and feed capacity is high. Sulfur contaminants emission and sulfur
management is an important challenges from environmental and economic viewpoints.
So, a small improvement in efficiency, operational cost and energy management in sulfur
recovery units is worthy. Generally, the Claus process comprises two main stages
including thermal and catalytic sections. In the first stage, a part of inlet H 2 S is burned in
a furnace at high temperature and elemental sulfur, sulfur dioxide and water vapor are
produced. After sulfur condensation, furnace effluent is fed to the catalytic stage. In the
catalytic stage, un-reacted hydrogen sulfide and produced sulfide dioxide react to form
elemental sulfur and vapor. Due to importance of hydrogen sulfide as one of the main
environmental pollutants, many researchers have focused on sulfur recovery from
hydrogen sulfide and other sulfur contaminants. Some scholars studied kinetics of
thermal conversion of hydrogen sulfide at different temperatures and residence time.
Several researches have focused on identifying catalyst, mechanism of reactions, rates, and
catalyst de activation in the catalytic section. Generally, various catalysts such as metal
oxides were proposed for Claus reaction and decomposition of H 2 S. Between metal
oxides, vanadium oxide has presented better performance and attracted more attention.

DISCUSSION
The Claus process was invented in 1883 by English scientist, Carl Friedrich Claus. The
Claus is the most popular sulfur recovery process to produce elemental sulfur from
hydrogen sulfide. The considered Claus process in this research is Split-Flow type and
consists a furnace reactor and two series adiabatic reactors. The feed is divided in two
streams. The first stream is mixed with air and fed to the furnace, while the second part of
feed stream is injected at the middle part of furnace. In the furnace, a part of hydrogen
sulfide is converted to the sulfur and sulfur dioxide. To prevent sulfur condensation in the
pipelines and heat recovery from furnace effluent, the output stream from furnace is
cooled in a boiler, and the elemental sulfur is condensed and separated from furnace
effluent. In addition, since the hydrogen sulfide conversion is characterized by a large

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number of radical reactions; there fore, it is mandatory to freeze the reactive situation to
avoid re combination reactions. Usually, about 60–70% of the total amount of elemental
sulfur is produced in the thermal section. Then, the stream is heated and fed to the first
catalytic reactor. The outlet stream from first reactor is cooled in the boiler to separate
elemental sulfur and after heating is fed to the second reactor. Generally, the catalytic
recovery of sulfur consists three sub steps including heating, catalytic reaction, cooling
and condensation. The outlet stream from second reactor is fed to the boiler to separate
elemental sulfur and uncondensed part is sent to the separation section. Fig. 1 depicts the
schematic of Claus process.

CONCLUSION
In this research, the Claus Sulfur Recovery Unit was modeled based on the mass and
energy conservation laws at steady state condition. The process consists two main parts,
thermal conversion in furnace and catalytic conversion in two series adiabatic fixed bed
reactor. Comparison between simulation results and plant data proved the accuracy of the
developed mathematical model. In or der to maximize sulfur recovery, a single objective
optimization problem was formulated considering inlet temperature of furnace and
reactors, feed distribution and flow rate of air in the furnace as decision variables. The
simulation results showed that sulfur recovery is improved about 1.07% in the optimized
process compared to the conventional. In addition, higher temperature and lower oxy gen
injection in the furnace increase rate of hydrogen sulfide de composition, so hydrogen
production is improved about 129.5% at the optimal system. The simulation results proved
the performance of Straight-Through Process over Split Flow Process in the considered
domestic unit. Generally, applying obtained optimal values on the system increases
production capacity and decreases sulfur contaminant emission. In addition, the results

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showed that produced elemental sulfur in the auto-thermal reactor is about 1.54 kmol/h
that is improved about 5.18% compared to the conventional reactor. Thus, the auto-
thermal reactor is a good candidate as substitute for conventional adiabatic reactor in the
Claus process to decrease sulfur contaminants emission.

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