TO SIMULATE AND OPTIMIZE SULFUR RECOVERY UNIT USING

ASPEN HYSYS

BATCH 2017-18

Group Members: Seat No:

Dua Yousuf CH-17018

Taimoor Ahmed Khan Lodhi CH-17040

Bazil Ahmed Khan CH-17309

Iffat Sultana Farooqi CH-17310

Project Supervisor: Project-Co Supervisor:

Mrs. Tuba Siraj Ansari Dr. Faizan Raza

DEPARTMENT OF CHEMICAL ENGINEERING

NED UNIVERSITY OF ENGINEERING AND TECHNOLOGY

i
 CERTIFICATE

This is certify that the work in the project report “TO SIMULATE AND OPTIMIZE
SULFUR RECOVERY UNIT USING ASPEN HYSYS” is entirely written by the
following enlisted students under the supervision of Mrs. Tuba Siraj . This project is
submitted to the Department of Chemical Engineering, NED University of Engineering and
Technology for the fulfillment of the Bachelor’s Degree in Chemical Engineering.

Batch 2017-18, Group NO. 16

Group Members:

Name: Seat No:

Dua Yousuf CH-17018

Taimoor Ahmed Khan Lodhi CH-17040

Bazil Ahmed Khan CH-17309

Iffat Sultana Farooqi CH-17310

________________ ________________

Supervisor Co Supervisor

_______________ _______________

Examiner 1 Examiner 2

DEPARTMENT OF CHEMICAL ENGINEERING

NED UNIVERSITY OF ENGINEERING AND TECHNOLOGY

ii
 ACKNOWLEDGEMENT

At this very onset starting with the name of Almighty ALLAH, The most beneficial, most
merciful, Compassionate, and Gracious who allowed us to complete this project. We dedicate
our work to our beloved parents. It would have utterly impossible to initiate and complete
this project without their effortless supports, who unconditionally provided the resources of
our project. We would like to thank the NED University of Engineering and Technology,
Karachi for supporting us in the completion and compilation of our project.
Firstly, we feel honored to express our deepest thanks to Prof. Dr. Inayatullah Memon,
Chairman of the Chemical Engineering Department who allow us to do this project
We are hugely indebted to our internal project advisor Mrs. Tubs Siraj for her
enlightening suggestions and intellectual advice. His professionalism, guidance energy
thoughtfulness dedication, and inspiration and will serve us as an example in our professional
career. We would also like to thank Dr. Faizan Raza for his valuable and precious time and
guideline

iii
 ABSTRACT

This project is designed to simulate and optimize the Sulfur Recovery Unit. In natural gas
refinery feedstock contain impurities such as sulfur and nitrogen. During purification the
sulfur is conveted to H2S during hydrotreating.
In this report the available processes for the recovery of elemental sulfur from H 2S are
discussed and modified clause process is chosen as the best alternative among all process due
to its high recovery.
The major focus is on modeling and simulation to get highest recovery of sulfur with low
capital and operating cost.
Despite it’s simple process, the stability of sulfur in elemental form at different
temperature range and selection of best available process according to the composition of
feedstock and highest recovery is very complicated.The most attractive aspects of this
process is techno-economical analysis.
Note: More will be added after the completion of project

iv
Title Page No.

CERTIFICATE…………………………….………………………………………………….ii
ACKNOWLEDGEMENT…………………………………...……………………………….iii
ABSTRACT………………………………………...………………………………………..iv
TABLE OF CONTENT……………………………………………………………………….v
LIST OF FIGURES…………………………………………………………………….…….ix
LIST OF TABLES…………………………………………………………………...………..x
NOMENCLATURE AND LIST OF SYMBOLS………………………….…………….….xii
CHAPTER 1: INTRODUCTION …………………………………........................................1
1.1 CHEMISTRY OF ELEMENTAL SULPHUR …………………………….......................1
1.2 ROLE OF SULFUR IN GASOLINE QUALITY SPECIFICATION...……......................2
1.3 WORLDWIDE PRODUCTION OF ELEMENTAL SULFUR…………….....................5
1.4 ALLOTROPES OF SULFUR ………………. ………………………….....................….6
1.5 COMBINATION OF SULPHUR WITH OTHER PERIODIC ELEMENT ......................6
1.6 RECOVERY OF SULFUR …………………………………………......................…......6
1.7 DEVELOPMENT OF SULPHUR RING …………………………….........................…..6
1.8 ELEMENTAL SULPHUR …………………………………………….......................…..6
1.9 SOURCES OF SULPHUR …………………………………………….........................…6
1.10 ENVIRONMENTAL REGULATION AND ECO FRIENDLY ……..............................7
1.11 USES OF SULPHUR……………………………………………………........................8
1.11.1 Manufacture of rubber product gun powder and fungicide in plants ......................8
1.11.2 Utilization of sulphur in batteries ……………………….........................................8
1.12 MEASUREMENT OF SULPHUR IN REFINERY SECTOR ……….............................8
1.13 SULPHUR IN FERTILIZER INDUSTRY …………………………............................8
1.14 PROBLEM STATEMENT …………………………………………....…....................9
1.16 ACID GAS RAIN ……………………………………………………...........................9
1.17 OBJECTIVE …………………………………………………………….......................10

v
1.18 BACKGROUND OF STUDY ……………………………………………..………....10
CHAPTER 2: LITERATURE SURVEY…………………………………………...............12
2.1 WORLD PETROLEUM RESERVES…………………………………………...............12
2.2 SWEET AND SOUR CRUDE OIL ………………………………………............…….12
2.2.1 Sour gas …………………………………………………………….............………12
2.2.2 Major location of sweet crude oil…………………………...............................…...12
2.3 ACID GAS …………………………………………………………............……………12
2.3.1 Source of acid gas …………………………………………………….....................12
2.3.1.1 Natural gas ……………………………………………………..........……….13
2.3.2 Necessity Of Removing Acid Gas …………………………...................................13
2.3.2.1 Environmental protection agency ………………………….............................13
2.4 HYDROGEN SULPHIDE ……………………………………………...........………….13
2.4.1 Sources of hydrogen sulphide ………………………………...................................14
2.4.1.1 From Amine Treating Unit …………………………………...............……….14
2.4.1.2 From Sour Water Stripping Unit ……………………………..................……14
2.4.2 Uses Of Hydrogen Sulfide …………………………………………........................14
2.4.2.1 Sulfuric Acid And Elemental Sulfur Production………....................................14
2.4.2.2 As A Reagent …………………………………………………........………….14
2.4.2.3 Nuclear Power Plant …………………………………………...............……..14
2.4.2.4 As A Chemical Warfare ………………………………………….............…...14
2.5 SULFUR………………………………………………………………………..........…..15
2.5.1 Elemental Sulfur As Primary Product……………………..............................…….15
2.5.1.1 In Batteries ………………………………………………........………………15
2.5.1.2 Used In Matches ………………………………………………........………...15
2.2.1.3 In Explosive ………………………………………………………….......……15
2.5.1.4 Gunpowder ……………………………………………………………......…..15
2.5.1.5 Insecticide And Fungicide ………………………………………….................15
2.5.1.6 In Production Of Sulfuric Acid By Contact Process……..............................…16

vi
 2.5.1.7 Lowering The Soil pH With Sulfur ……………………..................…………..16
2.6 TAIL GAS AS BY-PRODUCT ……………………………………………….………...16
2.7 PAST, PRESENT, AND FUTURE OF RAW MATERIAL AND PRODUCT …….…..16
2.7.1 Sulfur As Primary Product ……………………...…………………….....................16
2.8 AVAILABLE PROCESSES FOR THE PRODUCTION OF SULFUR………………...17
2.8.1 Oxygen-Based Clauss Process ………………………………………….............….17
2.8.2 Clauss Oxygen- Based Process Expansion ………………..................………….....18
2.8.3 Richards Sulfur Recovery Process ………………………………..................…......19
2.8.4 Super Clauss Process ……………………………………………….........………...19
2.8.5 Modified Clauss Process ………………………………………………..........…….20
2.9 COMPARITIVE ANALYSIS AMONG DIFFERENT PROCESSES ……………….....22
CHAPTER 3: PROCESS DESCRIPTION ………………………………………………...23
3.1 PROCESS SELECTION ……………………………………………………………..…23
3.1.1 Advantages Of Modified Claus Process ……………………………...................….24
3.1.1.1 Highest Purity …………………………………………………................……24
3.1.1.2 Environmental Friendly …………………………….......……………….….....24
3.1.1.3 Low Capital Cost ………………………………………………………...……24
3.1.1.4 High Design Capacity ………………………………………………….……24.
3.1.1.5 Low Operating Cost ………………………………………………………......24
3.2 EQUIPMENTS ………………………………………………………………...….……24.
3.2.1 Thermal Reactor ……………………………………………………………........…24
3.2.2 Acid Gas Burner …………………………………………………………….....….25.
3.2.3 Combustion Air Blower ……………………………………………………............26
3.2.4 Waste Heat Boiler ………………………………………………………….......…..26
3.2.5 Sulphur Condenser………………………………………………………........…….27
3.2.5.1 Filters …………………………………………………………………….………27
3.2.6 Reheaters ……………………………………………………………………....…...28
3.3 PROCESS DESCRIPTION ……………………………………………………….…….29

vii
 3.3.1 Hydrodesulfrization Process ………………………………………….................…29
3.3.2 Sulfur Recovery Unit ………………………………………………................……29
3.3.2.1 Claus Section …………………………………………………….....………...30
3.3.2.1.1 Reaction Furnace ………………………………………………….......……30
3.3.2.1.2 Sulfur Condenser…………………………....................................................30
3.3.2.1.3 Catalytic Reactors …………………………………………………..........…30
3.4 PROCESS FLOW DIAGRAM………………………………………….....…………….31
CHAPTER 4 PROCESS MODEL ………………………………………………....………32
4.1 FUNDAMENTAL COMPONENTS SELECTION……………………………..........…32
4.2 PROPERTY PACKAGE SELECTION ………………………………………....……...33
4.3 UNIT MODEL SELECTION …………………………………………………....……...34
4.3.1 Thermal Reactor …………………………………………………………...........….34
4.3.2 Heat Exchanger ………………………………………………………….........……34
4.3.3 Seperator…………………………………………………………………......……..34
4.3.4 Catalytic Reactor…………………………………………………………................34
4.4 ASSUMPTIONS…………………………………………………………………...…….35
CHAPTER 5: MATERIAL & ENERGY BALANCES………………………………...…..36
5.1 MATERIAL BALANCE ……………………………………………………..…………36
5.1.1 Reaction Furnace ……………………………………………………........………..36
5.1.2 Ftrst Catalytic Reactor ………………………………………………...............…...39
5.2 ENERGY BALANCE …………………………………………………………………..42
5.2.1 Overall Energy Balance ……………………………………………….............…...43
5.2.2 Energy Balance On Burner …………………………………………............……...45
5.2.3 Energy Balance On Furnace …………………………………………............…….46
5.2.4 Energy Balance On Condenser-01 ……………………………………..............…..47
5.2.5 Energy Balance On Reheater-01 …………………………………..............……….49
5.2.6 Energy Balance On 1st Catalytic Reactor-01………………….................………...50
5.2.7 Energy Balance On Condenser-02 …………………………………..............……..51

viii
 5.2.8 Energy Balance On Reheater 02 ……………………………………...............…....52
5.2.9 Energy Balance On Second Catalytic Reactor …………………..............................54
5.2.10 Energy Balance On Condenser-03 ……………………................………………..56
REFERENCE...........................................................................................................................58

LIST OF FIGURES

Figure 1.1: Structure and properties of elemental sulfur ……………………………....……..2

Figure 1.2: Statics of sulfur in gasoline 2012 ………………………………………..……….3

Figure 1.3: Statics of sulfur in gasoline 2015……………………..…………………………..3

Figure 1.4: Statics of sulfur in gasoline 2025 ……………………………………….…….….4
Figure 1.5:Statics of sulfur in gasoline 2030 ………………………………………...…….....4
Figure 1.6: Word-wide production data ………………………………………..………...…..5
Figure1.7 Acid gas rain …………………………………………………………………..….10

Figure 2.1: Sulfur imports data forecast ………………………………………………….....17

Figure 2.2: Effects of O₂ conc on Claus plant capacity and reaction furnace temp ……........18

Figure 2.3: COPE process …………………………….…………………………………......19

Figure 2.4: Super clauses 99 and 99.5 processes………………………………………….....20

Figure 2.5: Modified Claus process ………………………………………………………....21

Figure 3.1: Consumption of sulfur worldwide ……………………………………………....24

Figure 3.2: Reaction Furnace …………………………………………………………….…26

Figure 3.3: Acid gas burner ………………………………………………………………....26

Figure 3.4: Waste heat boiler …………………………………………………………….….28

Figure 3.5: Schematic diagram of sulfur condenser.………………………………...……....29
Figure 3.6: Cross-sectional view of sulfur condenser showing multiple condensers…...…...29

Figure 4.1: Components ……………………………………………………………………..34

Figure 4.2: Property package selection ……………………………………………………...35

Figure 4.3: Composition of acid gas and sour gas …………………………………………..36

ix
Figure 5.1: Reaction furnace …………………………………………………………….…..39
Figure 5.2: First catalytic reactor………………………………………………………….…42

LIST OF TABLES

Table 1.1: Expected regional gasoline Sulphur content ………………………........……........3

Table 1.2 Worldwide production …………………………………………………….......…...4
Table 1.3: Typical properties of Sulphur…………………………………………….......…...7
Table 3.1: Comparison between different process ……………………………………..........22
Table 5.1: Molar flow rate calculation (R.F)………………………………………….....…..40
Table 5.2: Error Calculation (R.F) ……………………………………………………..........41
Table 5.3: Molar flow rate calculation (1ST C.R)……………………………………......…...43
Table 5.4: Error Calculation (1ST C.R) ……………………………………………….....…..44
Table 5.5: Names of streams…………………………………………………………......…..46
Table 5.6: Energy balance of stream 1………………………………………………….....…47
Table 5.7: Energy balance of stream 1………………………………………………….....…47
Table 5.8: Energy balance of stream 14……………………………………...........................47
Table 5.9: Energy balance of stream 15……………………………………...........................48
Table 5.10: Energy balance of stream 16………………………………….............................48
Table 5.11: Energy balance on burner inlet…………………………………………….....…48
Table 5.12: Energy balance on burner outlet ………………………......................................48
Table 5.13: Energy balance of stream 2( furnace inlet )……………......................................49
Table 5.14: Energy balance of stream 3(process air)…………………...................................49
Table 5.15: Energy balance of stream 4( t.r outlet)……………………………………....….50
x
Table 5.16: Energy balance on burner outlet(vapour)……………….....................................51
Table 5.17: Energy balance on condenser outlet( liq)…………………………………....….51
Table 5.18: Energy balance of stream 4 ……………………………………………….....….51
Table 5.19: Energy balance on reheater (inlet)…………………………………………....…52
Table 5.20: Energy balance on reheater (inlet) stream 6………………………………....….52
Table 5.21: Energy balance on reheater (outlet)…………………………………………......52
Table 5.22: Energy balance on reactor (01-inlet)…………………………………………....53
Table 5.23: Energy balance on reactor (01-outlet)………………………………………......53
Table 5.24: Energy balance on condenser (2-inlet)……...…………………………………..54
Table 5.25: Energy balance on condenser (2-outlet(l))…...…………………………………54
Table 5.26: Energy balance on condenser (2-outlet(v))……………………………………...55
Table 5.27: Energy balance on stream- 9…………………………………………………….55
Table 5.28: Energy balance on stream- 10…………………………………………………...55
Table 5.29: Energy balance on stream- 11…………………………………………………...56
Table 5.30: Energy balance on stream- 12…………………………………………………...56
Table 5.31: Energy balance on reactor (02-inlet)……...…………………………………….57
Table 5.32: Energy balance on reactor 02-inlet(stream 12)………………………………….57
Table 5.33: Energy balance on stream- 13…………………………………….......................58
Table 5.34: Energy balance on stream- 14…………………………………….......................57
Table 5.35: Energy balance on condenser 3 inlet (stream-13)……………………………….58
Table 5.36: Energy balance on condenser 3 inlet (stream-14)………………………………58
Table 5.37: Energy balance on condenser 3 outlet (stream-15)……………………………...59
Table 5.38: Energy balance on reactor 03-outlet(stream -16)………...……………………..59

xi
 NOMENCLATURE AND LIST OF SYMBOLS

SRU Sulfur Recovery Unit

⁰F Degree Fahrenheit
⁰C Degree Centigrade
COPE Claus –Based Process Expansion
RSRP Richard Sulfur Recovery Process
COS Carbonyl Sulfide
CS₂ Carbon disulfide
WHB Waste Heat Boiler
M.W Molecular Weight
V.D Vapour Density
V.P Vapour Pressure
B.P Boiling Point
O₂ Oxygen
H₂S Hydrogen Sulfide
R.F Reaction Furnace
T.R Thermal Reactor
HDS Hydrodesulfurisation

xii
 CHAPTER 1

INTRODUCTION

1.1 CHEMISTRY OF ELEMENTAL SULPHUR

The term elemental sulfur comes from a latin word that means “to burn”. Elemental
Sulphur is a non-metallic element and belongs to the group of oxygen group [VI A]
(chalcogen) of the periodic table that occurs naturally both in the combine and free state as
the most reactive element and is found as the thirteen most abundant element in the earth
crust and its proportion in the earth crust is found to be 0.03 to 0.06 %. Whereas the deeper
layer of the earth crust contains a great amount of sulfur in pure and crystalline form. The
percentage of sulfur in seawater is found to be 0.09 % and is mostly in the form of sulfate.
Sulfur due to its reactive nature can react with all the elements except gold and platinum
and thus can be used as a good source to extract metals and their compounds. Many ways and
technologies have been used to separate Sulphur in their elemental form to make the
environment safe from toxicity. The Claus process, modified clause, super clause, and Frasch
process extracts elemental sulphur using amine and sour glasses and gives the final product
in the form of elemental sulphur. The elemental sulphur has a wide scope of the study to
regulate environmental conditions.
Organic sulfur is also found in gasoline diesel and fuel oil as acidic sulphur.
(mercaptans)and non-acidic Sulphur as (thiophenes, sulfides, and disulfides). Elemental
sulphur is mostly found in diesel in diesel.
The Donahue describes the summary of the structure of the Sulphur and its allotropes.
Schmidt reviewed the general properties of sulfur and eight new metastable allotropes.
Harris discovered the properties of malt. The main purpose of this study is to enhance or
optimize the amount of elemental sulphur. [1]

1
 Figure 1.1 Structure and properties of elemental Sulphur1.2

1.2 ROLE OF SULPHUR IN GASOLINE QUALITY SPECIFICATION

The greater part of the oil-based commodities centers around the wide utilization of fuel
with incredibly low sulfur content. The major focal point of the US in 2004 was to diminish
the concentration of sulfur up to 80 ppm per gallon. But in year 2000 the US brought down
the substance of sulfur up to 30 ppm for all refineries. The most brought down determination
is set by California till 15 ppm.

2
 Table 1.1 Expected regional gasoline sulphur content
REGION 2012 2015 2020 2025 2030

US AND CANADA 30% 30% 10% 10% 10%

LATIN AMERICA 520% 255% 130% 45% 30%

EUROPE 13% 10% 10% 10% 10%

MIDDLE EAST 605% 235% 75% 25% 16%

FSU 315% 115% 35% 20% 12%

AFRICA 795% 493% 245% 165% 95%

Role of gasoline quality specification - 2012

1000
S production (Metric tons)

800
600
400
200
0
US AND Latin America Europe Middle Africa
CANADA
Name of regions

Figure 1.2: Statics of sulfur in gasoline 2012

3
 Role of gasoline quality specification - 2015
600

S production (Metric tons

500
400
300
200
100
0
US AND Latin America Europe Middle Africa
CANADA

Name of regions

Figure 1.3: Statics of sulfur in gasoline 2015

Role of gasoline quality specification - 2025

100
S production (Metric tonse

80
60
40
20
0
US AND Latin America Europe Middle Africa
CANADA
Name of regions

Figure 1.4: Statics of sulfur in gasoline 2025

Role of gasoline quality specification - 2030

100
S production (Metric tons

80
60
40
20
0
US AND Latin America Europe Middle Africa
CANADA
Name of regions

Figure 1.5: Statics of sulfur in gasoline 2030

4
1.3 WORLDWIDE PRODUCTION OF ELEMENTAL SULPHUR (METRIC TONS)
Table 1.2 Worldwide production [2]
Region of world 2012 2015 2020 2025 2030
producing sulfur
US AND CANADA Column1 Column2 Column3 Column4 Column5
Latin America 30 30 10 10 10
Europe 520 255 130 45 30
Middle East 13 10 10 10 10
Africa 605 235 75 25 16
795 493 245 165 95

WORLDWIDE
PRODUCTION (METRIC TONS)

PRODUCTION DATA
12,000
10,000
8,000
6,000
4,000
2,000
0

NAMES OF COUNTRIES
Figure 1.6: World wide production data [3]

5
1.4 ALLOTROPES OF SULPHUR
1) Monoclinic (beta)
2) Rhombic(alpha)
3) Gamma

1.5 COMBINATION OF SULPHUR WITH OTHER PERIODIC ELEMENTS

Sulfur combines with other elements as sulphides of copper-zinc, iron, lead, and as
sulfates of barium, calcium magnesium, and sodium, etc.

1.6 RECOVERY OF SULFUR

The 'Frasch' measure which is essentially a mining strategy first sulfur recover process
recuperates up to 75% to 92 % sulfur which gets recoverable during activity.

A half of capacity material of sulfur is available in the USA, Canada, Japan France,
Poland, and Mexico are the significant sulfur exporters of the world.

1.7 DEVELOPMENT OF SULPHUR RINGS

The form of sulfur naturally occurs in three forms that are S2, S6, and S8, as the
temperature increases the S8 rings will polymerize themselves into other forms of sulfur The
transition between different forms of sulfur occurs naturally and in different forms by
utilizing the enthalpy of reaction. With a high-temperature reaction, the S6 and S8 rings open.

1.8 ELEMENTAL SULFUR

From the oil and gas production, sulfur that is recovered or mined is known as brimstone
or elemental sulfur.

1.9 SOURCES OF SULPHUR

The major and the secondary sources of sulfur are S0₂ and H₂S. The sources of S0₂ is
industrial water and flue gases while the major source of H₂S is obtained from the sour
natural gas, petroleum refinery products and coke-oven natural gas.

6
 Table 1.3: Typical properties of sulphur

Chemical name Sulfur

Symbol S

Atomic number 16

Family name Elemental sulphur

Physical state Solid

Appearance Yellow-colored crystals

Odor Odorless and faint odor like rotten eggs

Purity 90% -100%

Vapor pressure 0 mm Hg at 280 ⁰F

Solubility in water Insoluble

Density 2.07 gm/cm3

Boiling point 832 ⁰F (444 ⁰C)

Flashpoint 405 ⁰F

1.10 ENVIRONMENTAL REGULATION AND ECONOMICAL FRIENDLY

The demand for SRU in the oil and gas sector is increasing day by day as it decreases
the emission of SO2 and ammonia rejection in the environment by making it
environmentally friendly and converts waste into treasures by producing elemental sulfur.
As environmental regulations have become more demanding according to the present history
of WHO (World Health Organisation) the emission of SO2 into the air is hazardous as it
produces acid gas rain which causes deforestation and decreases the emission of nitric acid in
an environment otherwise which will cause severe irritation to eyes, mucous membrane
bronchitis and are highly corrosive which when is therefore, we are converting it into
elemental sulphur and it recycles the H2S back to the unit.
The H2S (Hydrogen sulfide or hydro sulphuric acid) is one of the most toxic corrosive
acid gasses so it should not be released into the environment.

7
 For environmental regulation control, it also regulates and the SRU unit. One of the most
demanding eco-friendly and optimized units as it optimizes the production of sulfur by using
modified claus process. [4]

1.11 USES OF SULPHUR

1.11.1 Manufacture of Rubber Products Gun Powder, And as a Fungicide in Plants

Sulfur is a component most generally utilized as a solidifying specialist in the assembling

of elastic items like tires. Sulfur accepted significance because of its broad use in sulfa
medications and skin treatments. Sulfur is additionally utilized in the assembling of matches,
vulcanized elastic colors, and black powder. In a finely separated state and much of the time
blend in with lime, sulfur is utilized as a fungicide on plants. It is a finely partitioned state
and much of the time blended in with lime. Corrosive sulfur is perhaps the most significant
of all modern since it is utilized on the sulfur containing particles as well as in the production
of various other material that doesn't themselves contain sulfur like phosphoric corrosive.
.

1.11.2 Utilization of sulfur in batteries

The Li-S battery is a sort of powered battery having high explicit energy about 18000
KJ/kg. These batteries were utilized in the longest and most elevated height automated
sunlight-based fueled plane flight. The utilization of sulfur expands the expense of the
battery.

1.12 MEASUREMENT OF SULPHUR IN REFINERY SECTOR

The study of Sulphur is of a wide scope, the unit for the measurement of Sulphur is TS.
The total Sulphur is measured with elemental combustion analyzer or by detection technique
or micro volumetric technique in the refinery sector both acidic and non-acidic impurities are
present in Sulphur. The acidic sulfur compounds include thios, sulfides and disulfides are
examples of non-acidic Sulphur compounds. The Sulphur is removed from the petroleum
distillate to reduce CO₂ emission when fossil fuels are combusted to protect catalysts in the
refining processes as the presence of hydrogen blocks the pores of the catalyst making its
deactivation. The main process of removing Sulphur is by the use of a hydrotreating process
in which H₂S is recovered in the end.

1.13 SULPHUR IN FERTILIZER INDUSTRY

Sulfur is produced in the fertilizer industry is mainly used for
1) Increasing the sulphur deficiency rate.
2) Growth in demand for crops to result in a Sulphur deficiency.
3) Sulfur emission regulations driving demand for added Sulphur.
4) High consumption of traditional sulfate fertilizers to drive the market growth.
8
1.14 PROBLEM STATEMENT
H2S is both an irritate and a chemical asphyxiant the which affects the central nervous
system its low concentration can irritate the eyes nose throat and respiratory system level of
H2S above 10ppm is extremely dangerous to life and health and causes severe, extreme level
of H₂S concentrations can cause severe headache and respiratory illness.
The hydrogen sulfide gas is heavier than air and can travel down to the ground in the oil
and gas sector the SRU unit is in high demand as it diminishes the toxicity of H 2S which
starts becoming hazardous at 10ppm which is a toxic flammable colorless and odorless gas

1.15 ACID GAS RAIN

The main reason for the formation of acid gas rain is the chemical reaction that is caused
when nitrogen and carbon-di-oxide releases from any process reacts in an environment where
it mixes with oxygen and water to form more acidic pollutants known as acid rain as a result
of which these compounds can travel at a long distance resulting in rain, snow and fog.
Hence the efficiency of Sulphur recovery process minimizes the formation of acid gas rain up
to a great extent. [5]

Figure1.7 Acid gas rain

9
1.16 OBJECTIVE
Our objective of this project is to optimize the production of a Sulfur recovery by varing
different temperature and pressure conditions here in which we are using two allotropes of
Sulphur that is S₂ and S₈ which are the most stable allotrope of Sulfur. For this purpose, we
are using the modified clause process among all processes as this process has the highest
efficiency and will do the case study on types of equipment of SRU for the attainment of
maximum efficiency.

1.17 BACKGROUND OF STUDY

Production of sour natural gas and higher sulfur content crude oil has been increasing in the world
and new technologies are emerging to recover Sulphur from H2S from these valuable products.

The natural gas deposits and crude oil deposits (rock shell) obtained from reservoirs contains
many impurities which increases the pH and make the gas toxic in order to avoid corrosion ,poisoning
and fouling and to make this gas environmental acceptable, it is sent through different operations
which contains different number of purifying stages. One of the major and economical purifying
process is SRU.

The Sulphur recovery unit is a major regulatory unit of the oil and gas sector and natural gas
consumption sector process for the production of elemental Sulfur by the reaction with H 2S and S02.
The SRU unit plays a large role in refinery processing, different methods have been employed to
recover elemental Sulfur from natural gas and diesel oil. The modified clause process has been
considered the most significant and economical method for recovering elemental Sulphur from
desulphurization (invented by an English scientist name carl fried rich clause a germen company I.G
fare industry A.G) This is the rich acid gas method where most of the H2S is converted before going
into the catalytic section are used to maximize Sulphur recover efficiency.

In our process we are using modified claus process which is one of the major process for the
conversion of H2S in elemental Sulfur .The end product will be Sulfur , water and thermal energy

The clause process is divided into two main sub processes

1. Thermal process (includes burner, conversion reactor)

2. Catalytic process.

The Sulphur plant producing liquid Sulphur consist of the degassing section and tail gas recovery
unit (TGTU).

10
11
 CHAPTER 2

LITERATURE SURVEY

2.1 WORLD PETROLEUM RESERVES

According to the record, in January 2013, the reserves of 1.6 billion barrels of crude
petroleum. The total oil reserves in OPEC are 73.6 % of total oil reserves.
The largest heavy sour crude share in the world is Venezuela with total reserves of 18%.
After Venezuela, Saudi Arabia has the biggest oil reserves with 16.2%, Iran 9.4%, Iraq 9.6%,
and Canada 10.6%, [6]
2.2 SWEET AND SOUR CRUDE OIL
The crude oil obtained from reserves is sour. The amount of sulfur decides whether the
crude is sour or sweet. If the amount of sulfur is less than 0.5% the crude oil is sweet and if
the amount of sulfur is greater than 0.5% then the crude oil is sour. [6]
2.2.1 Sour Gas
Sour gas is the natural gas containing H2S and CO2 as impurities in it. The presence of
H2S and CO2 makes it sour gas.
2.2.2 Major Location of Sweet Crude Oil
The major location of sweet crude oil in the Appalachian Basin in Eastern North
America, the North Sea of Europe, North Africa, Australia, and Indonesia.

2.3 Acid Gas

Acid gas is a mixture of CO₂ and H₂S contain a small number of water vapors and
hydrocarbon gases. The amount of H2S can be higher in acid gas as compared to the amount
of CO2. Acid gas is a colorless gas having no odor. It is extremely flammable and explosive.
A low concentration of this gas (less than 100ppm) causes respiratory irritation. A
concentration greater than 1000ppm will cause immediate unconsciousness and death
through respiratory paralysis.

2.3.1 Source of Acid Gas

12
2.3.1.1 Natural Gas
In 1875 Britain produced natural gas or methane gas from coal and used it in the gas
lamp. In modern times the first drill internationally to obtain natural gas was drilled in 1821
in Fredonia, NY. Initially, it was found below 27ft depth when drilled by William Athwart to
get the high pressure of the gas.
Raw Natural gas obtained from a well is called wet natural gas because it contains
impurities, contaminants, acid gas, water vapor, and some other undesired component. To
remove these impurities natural gas is processed through different processing units. Firstly, at
the collection point, it is sent to a separator vessel where free liquid water and Condensate of
natural gas are removed. The natural gas is then sent to an oil refinery where the first step is
the removal of acid gas. There are many processes available for acid gas removal e.g., amine
treating when the natural gas becomes purified and all the impurities removed and only
contain methane (CH₄) is called dry natural gas.
2.3.2 Necessity Of Removing Acid Gas
Acid gas can cause damage, corrosion, and rusting to the pipeline and the equipment
result in shortens the lifespan of both pipeline and equipment and can cost millions to replace
these pipelines.In addition to its corrosive nature acid gas can cause serious health
complications in humans. Due to their dangerous nature acid gas must be highly controlled.
In past, gas producers were incinerated or flare the acid gases into the atmosphere but due
to environmental concerns and due to the growing SO₂ emission of a small amount of acid
gas to the surrounding is prohibited that’s why H₂S removed in the refinery from the acid gas
removal section is recovered.
2.3.2.1 Environmental Protection Agency (EAP)
In the US the standard for SO₂ is set in 2010, the quantity of SO₂ in the air is 75 parts per
billion for 1 hour. When SO₂ is combined with H2O it forms H2SO4 which is the main
constituent of acid gas.
2.4 HYDROGEN SULPHIDE
H2S is also known as sulphurated hydrogen or stink damp. It is present in crude oil and
natural gas along with CO2 (acid gas). It cannot be discarded into the environment due to its
toxic nature. The feedstocks for the sulfur recovery unit are acid gas that is obtained from the
ATU (Amine Treating unit) and sour gas is obtained from SWSU (sour water stripping unit).
Both the gases contain a significant amount of H₂S and other acidic gases. H₂S is colorless
and very explosive with an odor like a rotten egg. Its boiling point is -60.4⁰C and the freezing
point is -85⁰C. When it is burnt in presence of oxygen, it burns blue, forming sulfur dioxide
and water. [7], [8]

13
2.4.1 Source of Hydrogen Sulfide
The feedstocks are acid and sour gas containing Hydrogen sulfide and other gases
coming from the Amine Treating Unit and Sour Water Stripping unit.
2.4.1.1 From Amine Treating Unit
An Amine Treating Unit having a packed column or tray is used for separating hydrogen
sulfide from acid gas. From the top of the tower in a packed column lean amine is circulated
by using a pump and gas is introduced from the bottom of the column. The hydrogen sulfide
gets adsorbed by lean amine and as a result, sweet gas is obtained leaving from the top and
lean amine becomes rich amine flows through the bottom by gravity. On the regeneration of
amine to remove hydrogen sulfide by heating with the help of a reboiler, hydrogen sulfide
goes to the sulfur recovery unit from the top of the column while lean amine is obtained from
the bottom.
2.4.1.2 From Sour Water Stripping unit
The sour water stripping unit consists of a tray column and reboiler. Pre-heated sour
water is introduced into the stripper, H₂S gets separated from water by heating with the help
of a reboiler. The H₂S gas leaving from the top goes to the sulfur recovery section while the
bottom product from the column that is the water goes to the stripped water storage tank to
reuse for internal circulation.
2.4.2 Uses of Hydrogen Sulfide
Hydrogen Sulfide has a reflective ratio close to air which makes it difficult to detect with the
human eye. Despite being flammable and reactive gas, there are quite a few ways in which it
can be utilized.
2.4.2.1 Sulfuric Acid and Elemental Sulfur Production
The principle use for H2S is in the creation of sulfuric acid and essential sulfur. Sulfuric
acid is used in fertilizers and making several chemicals. [9]
2.4.2.2 As a reagent
It is beneficial on the grounds for the preparation of different types of reduced sulfur
compounds. The reagent is a starting compound of a chemical reaction. [10]
2.4.2.3 Nuclear Power Plants
In nuclear power plants, H₂S is used in the production of heavy water, an option in
contrast to regular water that empowers nuclear reactors to utilize standard uranium fuel. [10]
2.4.2.4 As Chemical Warfare
H₂S is also used in chemical warfare. Modern industries, like iron smelters, food
processing plants, and landfills produce or use hydrogen sulfide. [10]

14
2.5 SULPHUR
Sulfur is a nonmetallic element of group 16 in the periodic table. Pure sulfur has the
following properties which are tasteless, odorless brittle solid that is yellow, a poor conductor
of electricity, and insoluble in water. It also forms a compound with a non-metallic element.
It reacts with all-metal except gold and platinum forming sulfide which is considered as a salt
of H₂S.
In oil and gas refineries sulfur is considered as an undesired element that is present in
crude, natural gas, and petroleum in the form of H₂S so it is recovered to elemental sulfur
using the Claus process.
2.5.1 Elemental Sulphur As Primary Product
A large amount of Elemental sulfur is produced in refineries as a side product which is
undesired for refineries. But elemental sulfur has many uses in other fields. The sulfur
obtained by crude petroleum oil and acid gas recovery is in the molten state which is then
converted to solid form (block) or pellets that can be easily transported. Its major uses are in
the manufacturing of H₂SO₄ whereas it’s also used in the fertilizer industry, in batteries, in
the lab as an analytical reagent, in detergent, in matches, in explosives, in black gun powder .
2.5.1.1 In Batteries
The Li-S battery is a type of rechargeable battery having high specific energy
18000KJ/kg these batteries were used in the longest and highest altitude unmanned solar-
powered airplane. The use of Sulphur decreases the cost of the battery.
2.5.1.2 Used In matches

Sulfur is the second essential ingredient in a match in which it acts as a fuel. The head of
safety matches is made up of an oxidizing agent such as potassium chlorate (KClO₃) mixed
with sulfur, filler, and glass powder. Sulfur has a good burning ability.
2.5.1.3 In Explosive
Sulfur is used as a plasticizer in explosives and organic explosives mixtures such as black
powder, flash powder the elemental sulfur are used as a fuel component.
2.5.1.4 Gunpowder (Black Powder)
There are three main components of gunpowder nitrate, charcoal, and sulfur. Sulfur
increases the rate of Combustion and it acts like fuel.
2.5.1.5 Insecticide and Fungicide
Sulfur kills fungi, it reacts with plants or fungi to produce a toxic agent or it may work by
entering the fungi cell and affecting cell respiration. Sulfur can kill insects if they eat sulfur
or even touch sulfur. It also affects body function by altering the ability to produce energy.
Sulfur is generally used in crops to combat fungal disease and post-harvest fungal disease.

15
That is controlled by sulfur including brown rot, scab, mildew, powdery mildew, leaf spot,
and rusts.
2.5.1.6 In the Production of Sulfuric Acid by Contact Process
Sulfur is oxidized to SO₂ by burning in presence of air. Sulfur dioxide is then converted
to SO₃. In the presence of V₂O₅ catalyst and then in the absorption tower SO₃ is absorbed into
H₂SO₄ to form oily liquid “oleum” (H₂S₂O₇). The oleum is then added to water to form
sulfuric acid.
2.5.1.7 Lowering The Soil pH With Sulfur
Some plants like blueberries grow under low pH. The addition of elemental sulfur to the
soil to decrease the pH of soil is the cheapest way. If the soil pH is greater than 5.5 then the
addition of Elemental sulfur inappropriate amounts can decrease the soil pH up to 4.5. The
bacteria present in the soil convert elemental sulfur to sulfuric acid so that the PH of the soil
decreases. But the temperature of soil should be above 55⁰F because the bacteria are not
active under low temperature so the addition of Elemental sulfur is not suitable or useful in
the winter season or the areas where the temperature is low. The soil should not be flooded
i.e: anaerobic then the sulfur converted to H₂S (rotten egg smell) by anaerobic bacteria which
damage or kill the plant roots.
FeSO₄ is also used to decrease soil pH but it’s more costly than sulfur and a greater
quantity is required than elemental sulfur. Aluminum sulfate also acidifies but it's toxic.
.2.6 TAIL GAS AS BY-PRODUCT

Tail gas is obtained as a side product of the Claus unit in the form of off-gas. It contains
SO₂, H₂S, CS₂, COS and hydrocarbons. In the tail gas section, these gases are combusted and
converted into H₂S.

2.7 PAST, PRESENT, AND FUTURE OF RAW MATERIAL AND PRODUCT

2.7.1 Sulfur as Primary Product

16
 SULFUR IMPORTS FORECAST
7.00E+07
IMPORTS QUANTITY (KG) AND VALUE (US$)

6.00E+07

5.00E+07

4.00E+07

3.00E+07

2.00E+07

1.00E+07

0.00E+00
2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022 2023 2024

YEAR
VALUE QTY Linear (VALUE) Linear (QTY)

Figure 2.1: Sulfur Imports Data Forecast [11]

2.8 AVAILABLE PROCESSES FOR THE PRODUCTION OF SULFUR

2.8.1 Oxygen-Based Claus Process:
In the early 1970s, the oxygen-based Claus process has been used, the main objective of
this process is to increase the flame temperature of the reaction furnace. In this process, H₂S
content is below 10% used in process acid gas. With the help of air which is the source of
oxygen are used in this process as shown by the following reaction:
H₂S + ½O₂ = H₂O + S ………………………………………..Equation2.1
For elemental sulfur, we have to react 50 moles of O₂ with 100 moles of H₂S. In the tail
gas (300moles) containing (100 moles) of water and (200 moles) of N₂. O₂ can replace some
or all the air to reduced or eliminated N₂ content in the tail gas. [12]
The oxygen-based Claus process is divided into three enrichment:

1- Low-level oxygen enrichment (<28 vol% O₂ )

2- Medium level oxygen enrichment (28 to 45 vol% O₂)

17
3- High-level oxygen enrichment (> than 45 vol% O₂).

Figure 2.2: Effects of O₂ concentration on % Claus plant capacity and reaction furnace
temperature [12]

2.8.2 Claus Oxygen-Based Process Expansion (COPE)

This Claus process was modified by using recycle blower and the specialized R.F. The
reaction furnace temperature increased by the combination of combustion air with oxygen.
When the O₂ content of the air reaches up to forty-five vol %, so for the rich gas feed, the
max temp of 2700 ⁰F – 2900⁰F can be used, the COPE process recycles cool gas from
downstream of the first condenser back to the reaction furnace to avoid the exceeding temp
limitation. We have to increase the amount of recycling accordingly when the level of O₂
enrichment is increased. We will not face so much increase in temperature although 100%
oxygen is possible with the COPE process. We will understand the process by the following
diagram.

Feed gas, Reaction

2ND 3RD To Tail Gas
And furnace with 1st Converter
Converter Converter Unit
oxygen WHB

Figure 2.3: COPE Process [12]

18
 In its first commercial application, 85% capacity can be achieved in the COPE process.
With a rich acid gas feed in a refinery Claus amine tail gas unit, the oxygen causes the low
Claus plant pressure drop but its capacity is increased on the order of 100%. For a large
capacity increase, we must replace or modify waste heat boiler and the downstream first
condenser, so its design capacity can be exceeded.
When the leaner acid gases typically occurred, then the COPE yields more capacity in
gas field application. When the H₂S in the acid gas feed more than 60% then a small fraction
of the total pressure drop can be contributed by the thermal conversion section.
Eleven COPE units were functioning in the year 1995. [12]

2.8.3 Richards Sulphur Recovery Process (RSRP)

In 1982, a scientist named Kerretal disclosed the modification in the Claus process that
it can be operated at elevated pressure. In this operation, we used pressure 70psi to 300 psi
and for the cooling medium, we used a catalyst that was immersed in circulating liquid
sulfur. In RSRP, the best part is that the catalytic oxidizer replaced the combustion furnace in
the Claus plant. To maintain the temperature of about 700 ⁰F – 800 ⁰F, we sprayed cool liquid
sulfur with H₂S (partially oxidized) in feed gas over the catalyst bed. This process was first
tested in a lab and after the successful result theoretical design of a plant was proposed and
named as Richard Sulfur Recovery Process.

2.8.4 Super Claus Process

In (1988-1994), Comprimo has developed this process in which he worked on the
enhancement of sulfur recovery capabilities by reducing its inherent thermodynamics
limitation. In this process, direct oxidation reaction(equation-2.3) is used instead of reversible
Claus reaction (equation-2.2).
2H₂S + SO₂ = 2H₂O + 3S -------------------------------------------------------------Equation 2.2
H₂S + ½O₂ = 2H₂O + S ----------------------------------------------------------------Equation 2.3
In this process, we used a catalyst that consists of silica substrate supporting iron and
chromium oxide or alpha-alumina in the last converter of the Claus unit. By the use of this
technology, we get an 85% conversion of H₂S to elemental sulfur. Although the presence of
excess air, the concentration of SO₂ is low. No oxidation of CO, H₂, and COS or CS₂ cannot
be formed in this process. The Super Claus process is divided into two processes namely;
SUPER CLAUS 99 and SUPER CLAUS 99.5 processes. [12]

19
 Feed gas Superclaus
Combustion st Superclaus99
And 1 reactor 99.5 incinerator
chmaber section
air section

Figure 2.4: Super Claus 99 and 99.5 processes. [12]

2.8.5 Modified Claus Process
The Modified Claus process has two sections namely; the Thermal section and the
Catalytical section. The thermal section consists of waste heat boiler and the reaction
furnace. SO₂ and H₂O are produced in the burner reactor when the H₂S is burned with the
compressed air. In this type of reactor, we have two important variables which are the O₂ to
H₂S ratio and the temperature of the reactor. One-third stoichiometry ratio of O₂ to H₂S is
required for complete combustion of H₂S. Now the effluent gas which is coming from the
burner reactor is cooled in the waste heat boiler because it has to enter the catalytic reactor
for the conversion of H₂S and SO₂ into the elemental sulfur and water. To obtain elemental
sulfur and water, we have to introduce convertor effluent into a condenser unit. A small
quantity of sulfur is also produced in the burner reactor but with the help of waste heat boiler,
it may also be recovered. There are also used condenser to abstract the sulfur in this process
as shown in this process. [13]

20
Figure 2.5: The Modified Claus Process [13]

21
 2.9 COMPARATIVE ANALYSIS AMONG THE DIFFERENT PROCESSES
Table 3.1: Comparison between different processes

OXYGEN COPE RICHARDS SUPERCLAUS MODIFIED

BASED PROCESS SULPHUR PROCESS CLAUS
CLAUS RECOVERY PROCESS
PROCESS PROCESS

SOURCES FOR Oxygen Combustio High pressure By the use of Catalyst and use
REACTION n air with catalyst of two reactors
oxygen

TEMPERATUR 2,200⁰F to 2,700⁰F to 700⁰F to 800⁰F 2000⁰F 599⁰F to 626⁰F

E 3,400⁰F 2900⁰F

METHODS OF Combustion Combustio No heat is required Reaction furnace Burner reactor

HEAT air n air in this process burner
INTRODUCTIO
N
FOR
REACTION
CATALYST No catalyst is No catalyst Titanium-based Silica substrate Activated alumina
TYPE used is used catalyst supporting iron catalyst, promoted
and chromium titania catalyst
oxide or Alpha-
alumina
PRESSURE Negligible Pressure 70 to 300 psi SOLID Feed=8-11psi
pressure drop is SULPHUR we
proportiona get at
l to the Atmospheric Product=57-
square of pressure at 65psig
gas flow 95.5⁰C
rate
CONVERSION It is based on 85% 99% 99% -99.5% 99.8%
vol% of
oxygen

22
 CHAPTER 3

PROCESS DESCRIPTION

3.1 PROCESS SELECTION

Elemental sulfur can be achieved by the method of Modified Claus Process, it has two
Claus catalytic reactor systems to achieve sulfur by H 2S contained in the feedstock. In the
new amine treating unit and non phenolic sour water stripping unit, the feedstock shall be
acid and sour gases. Modified Claus process gives the highest purity of sulfur,
environmentally friendly, catalyst also recoverable, noise limitation and highest return on
investment as compared to other technologies. Many sulfur recovery plants have been
established due to the large consumption of sulfur, this chart shows the consumption of sulfur
among countries of the world. [14]

WORLD COMSUMPTION OF SULFUR -2020

china africa middle east

united states eastern europe central and south america
western europe southwest asia others

Figure 3.1: Consumption of Sulfur worldwide

23
3.1.1 Advantages of Modified Claus Process
3.1.1.1 Highest Purity
The modified Claus process has the highest purity among other processes.
3.1.1.2 Environmental Friendly
In this process, we made the gas environmentally friendly by extracting the sulfur.
3.1.1.3 Low Capital Cost
Overall capital cost is low, as we used few reactors and small process line diameters are
used in this process.
3.1.1.4 High Design Capacity
This process has a design to handle 5457 lb/hr. of acid gas (feedstock) which produces
4780 lb/hr. liquid sulfur (product).
3.1.1.5 Low Operating Cost
As we only purifying the gas so it does not take so much energy consumption and the
catalyst is also recoverable and reusable during the process
3.2 EQUIPMENT USED IN RECOVERY OF ELEMENTAL SULPHUR BY CLAUS
PROCESS
3.2.1 Thermal Reactor or Furnace
The acid gas is first fed to the thermal reactor or furnace where it is combusted in the
presence of air. The reaction that takes place in the furnace is
H2S + 1.5 O2 → SO2 + H2O --------------------------------------------Equation 3.1
In our simulation, we use a Conversion reactor as the reaction furnace. Experimentally,
the thermal reactor consists of a horizontal carbon steel vessel, and from protection from the
high temperature, it is equipped with multiple refractory layers. In the reaction furnace, one-
third of the H2S is combusted to SO2.

24
 Figure3.2: Reaction furnace
3.2.2 Acid Gas Burner
Before entering the thermal furnace, acid gas is heated in the burner named acid gas
burner to make the combustion process efficient. The turbulence is created for good mixing
of acid gas with process air using high velocities with the same flow rate design for air and
acid gas. The velocities should not be lower than the desired amount as it can cause a
decrease in turbulence which is necessary for better mixing of gas with process air so that the
combustion of acid gas will be efficient and complete.

Figure 3.3: Acid gas burner

25
3.2.3 Combustion Air Blower
The combustion air blower is present to generate air which is used as a source of oxygen
in the combustion of acid gas. Two types of the blower can be used [15]
1. Centrifugal compressor blower
2. Positive displacement blower

3.2.4 Waste Heat Boiler (Heat Exchanger)

The effluent gas from the thermal reaction furnace is sent to the waste heat boiler or heat
exchanger to cool down from 1350 C to 350 C by exchanging heat with water and generating
very high-pressure steam.
The heat exchanger is used here as a waste heat boiler which is a fire tube and kettle type
boiler. The combusted gas is on the tube side while on the shell side water is converted to
steam by taking heat from combustion gas. The tube is made up of carbon steel and arranged
in a square-type pitch to prevent the pressure drop. The shell side and outlet channel side are
insulated to prevent heat loss to the environment. The refractory used for insulation should be
selected properly so that the casing or shell side remains hot or above the Sulphur dew point.
[16]
A two-phase boiler through a single pass design can be used in place of a kettle type
boiler. Tube inlet and tube sheet region is cooled by using ferrules or ceramic at the tube
inlet. Economizer is not used here to prevent tube side corrosion due to low temperature. The
outlet streamside is a nozzle with a demister.

Figure3.4: Waste heat boiler

26
3.2.5 Sulphur Condensers
The condenser is placed after the Claus reactor to cool down the sulphur below the
Sulphur dew point to condense the elemental sulphur. Sulfur condensers are shell and tube
heat exchangers with kettle type. On the shell side, water is present which is exchanging heat
from the process gas and the water is converted to low or medium pressure steam. Tubes of
the condenser are 1-3 degrees sloped toward the outlet. The tube material is carbon steel.
The condenser shell side, inlet, and outlet are insulated by wood. The melting and
boiling point of elemental Sulphur is 119 ⁰C and 444.6 ⁰C. The ideal condenser temperature
is about 10 ⁰C above the Sulphur dew point.
To avoid cooling of liquid Sulphur, the liquid Sulphur outlet nozzles are jacketed. It also
increases the followability of liquid Sulphur. Demister or disengagement section is present at
the steam outlet nozzle to separate liquid sulphur from the process gas. [16]
3.2.5.1 Filters
To prevent dust, carry over in Sulphur run down lines steam jacketed filter is used at the
outlet of Sulphur condenser. To prevent the solidification of Sulphur the drains are kept
warm. A collection vessel is present to store liquid elemental sulfur produced. The level of
the vessel checks and maintain by the level controller. The sulfur is continuously removed
from the vessel.

27
 FIG 3.5: Schematic diagram of Sulphur condenser [16]

FIG 3.6: Cross-sectional view of a Sulphur condenser showing multiple condensers

integrated with a single shell. [16]

3.2.6 Reheater
Direct fired or fuel gas re-heaters are used after condenser to heat the process gas and
increase its temperature to the clause catalytic reactor temperature so that reaction can take
place in the forward direction.
28
 3.3 PROCESS DESCRIPTION

3.3.1 Hydrodesulfurization Process

The HDS process is a typically catalytic process used for the removal of sulfur from
refined and gas products.

The process of desulphurization is the removal of sulfur from lighter refinery cuts such as
diesel naphtha and vaccum gas oil. The crude oil with higher viscosity and higher densities
contain a higher amount and more complex sulfur compounds. Since the aliphatic and
Acyclic sulfides (thioesters) and cyclic sulfides (thiolates)) are easier to remove from
hydrodesulfurization or by thermal treatment but the sulfur present in aromatics (thiophenes.
g. benzothiophene, dibenzothiophene, benzo naphtho thiophene) are more resistant to sulfur
removal by hydrodesulfurization.

In the hydrotreater, the reaction occurs on an fluidized bed reactor. The reaction occurs
on an aluminum-based catalyst and is absorbed in:

● Molybdenum and cobalt (Como catalyst)

● Molybdenum and nickel (Nimes catalyst – added to Como when feedstock contains high
levels of chemically bound nitrogen)

The feeds (olefins free) are pumped with the recycling of hydrogen-rich gas. Then heat
exchanger is used to heat the combined feed. Fired heater is used to heat the mixture until the
mixture feed is vaporized and achieve the operating condition of a fixed catalyst bed where
the reaction of desulfurization occurred. The product streams are cooled using a heat
exchanger and the pressure is reduced using a pressure controller to bubble out the gasses
from the separator. The gasses bubbled out from the separator are acid gasses (H2S). These
gasses then go to the amine treatment unit to remove hydrogen sulphide. The stripper sour
gas (H₂S) consists of heavier hydrocarbons and the components like methane, ethane,
propane, and butane. Then from the amine treating unit, the sour gas (hudrogen sulfide) is
sent to the gas processing plant for the removal of hydrogen sulfide. For recovering
hydrocarbons are then send to series to the series of the distillation column. In the refinery fuel
gas system, we can utilize the remaining hydrocarbons, hence now the removed H2S is
converted into elemental sulfur in sulfur recovery unit.

3.3.2 Sulfur Recovery Unit

The SRU basically consists of three sections the first section is the thermal reactor section
or simply the Claus section. Claus section consists of two things, first is the thermal reactor
followed by the catalytic reactors in which the catalytic conversion takes place. The second
section is the liquid degassing section followed by the section in which the tail and other
ejected gases are vents off from the stack which is also installed in the unit. And the last
section is known as the solidification section or solidification package.

29
3.3.2.1 Claus Section
Claus section comprises the following units:
3.3.2.1.1 Reaction Furnace
The feed of the reaction furnace i.e: feed gas mainly consisting of components H2S, CO2,
and to a minor extent, various hydrocarbons are coming from amine-treating units and sour
water stripper. In a furnace burning of H2S takes place in the presence of air to form sulfur
dioxide and one-third of H2S is converted. The hot gas (process gas) from the combustion
chamber is quenched in the waste heat boiler before entering the sulfur condenser in order to
generate medium-pressure steam from high-pressure steam. As a result, 80 percent of the
heat released could be recovered as valuable energy.
3.3.2.1.2 Sulfur Condenser
The process gas from the waste heat boiler enters the first sulfur condenser where sulfur
is condensed, separated, and collected to the sulphur drum. Before entering the first catalytic
reactor, the process stream is pre-heated up to the optimum temperature for the catalytic
conversion in the first Claus reactor reheater.

3.3.2.1.3 Catalytic Reactors

In the First Claus Reactor, the catalytic conversion is carried out on an alumina catalyst
(10% of catalyst bed) and a titania catalyst (90% of catalyst bed). Hence the remaining
uncombusted two-third of the H2S and SO2 are reacted to form elemental sulfur. The catalytic
reaction is exothermic. The sulfur is recovered from there followed by the second catalytic
reactor. Now after the condenser there will be two outputs, the first is the tail gas, which
contains any unconverted gas to sulfur will be moved to the tail gas section which is known
as the tail gas treatment . And from the other condenser, the final sulfur is discharged from
there into the sulfur drum.

30
3.4 PROCESS FLOW DIAGRAM

31
 CHAPTER 4

PROCESS MODEL
A process is a set of actions carried out in series to achieve some results. Process
modeling makes the process representation useful and more simplified. Process modeling is a
major technique to organize things easily. The main objective of this modeling is to simulate
a major unit of the refinery sector that is the sulfur recovery unit in which a major portion of
sulphur is recovered in the form of elemental sulfur that is economically worthwhile. For the
simulation of this unit, we have used the software of Aspen hysys V10, which includes a
wide variety of property packages, mole palette, crude analysis, simulation environment.
This software is a major backbone of the polymer and refinery sector as all physical
processes can be easily simulated on this. It is used for both study state and dynamic
processes.
4.1 FUNDAMENTAL COMPONENTS SELECTION
The system components are the very first input to be fed while making a process
simulation. The system components include both conventional, non-conventional, pseudo
components, polymer components, and hypothetical liquids, etc. Aspen hysys includes a
wide variety of user-defined components that are called hypothetical components. If we are
dealing with such components that are not in the databank of aspen hysys then we have to
manually add it and specify its composition and weight etc.
The feed of the sulfur recovery unit includes a minute quantity of hydrocarbons and an
enhanced quantity of H2S and water for the reaction proceeding. The feed components are
pure and taken from the family of hydrocarbons included in component list 1.

32
 Table 4.1: Component list
COMPONENTS ALIAS
HYDROGEN H₂
WATER H2O
HYDROGENSULFIDE H₂S
METHANE CH₄
ETHYLENE C₂H₄
ETHANE C₂H₆
PROPANE C₃H₈
I-BUTANE i-C₄H₁₀
N-BUTANE n-C₄H₁₀
NITROGEN N₂
OXYGEN O₂
S2_VAPOR S₂
S8_VAPOR S₈
SULFURDIOXIDE SO₂

4.2 PROPERTY PACKAGE SELECTION (Fluid packages)

Following is the list of property packages that are used in a wide variety of simulation the
main purpose of the fluid package is to calculate the fluid thermodynamic properties of the
components of a mixture in the simulation environment (such as enthalpy, entropy, exergy,
density, vapor-liquid equilibrium). Aspen hysys is a product of aspen tech is one of the most
widely used modeling and simulation software in process engineering governing both steady-
state and dynamic processes. It provides a possibility to model a wide variety of processes
from distillation column design to reactors of various kinds, it also includes auxiliary
equipment that has been widely used in chemical and plant industries such as pumps,
turbines, evaporators, separators, heat exchangers etc. Generally, in Aspen plus we have two
environments the first environment is of properties in Aspen plus the components are to be
added and the methods according to the thermodynamic properties are to be chosen. The
second environment is called a simulation in which the material and energy streams are
added and the methods and processes are described according to the thermodynamics
properties that have been chosen. The property packages include Peng Robinson, equation of
state (EOS) used for the simulation of petrochemical oil and gas correlation.
For the next step select, on next and a new window will appear in this window we have to
select appropriate property models (Basis) for the process that is Peng Robinson which
expresses the fluid properties in terms of critical properties and acentric factor of each
species involved. The behavior of various species depends upon Peng Robinson.

33
4.3 UNIT MODEL SELECTION
4.3.1 Observations by Optimizing the Furnace (Thermal Reactor) Temperature
A Conversion reactor is utilized as a response heater for the fractional ignition of
hydrogen sulfide with oxygen to produces sulfur dioxide and water, the degree of the first
response is 25% in with the item as in the fume stage the subsequent response (endothermic
response) with the heat of reaction or standard enthalpy of reaction (12153.08 that happens
when a matter is changed by a given compound response
The adjustment in the arrangement of the level of S2 fumes was seen by eliminating and
burner and thus expanding the heap on heater dividers. The mix of burner and heater together
is made the thermal heater in which the burner sends the preheated combination of corrosive
gas and amine for additional ignition of response The recuperation of S2 without the burner
was found to exceptionally improved that was 92%. The heater works at high temperature
going from temperature around 1/third of the H2S is singed in the warm reactor.
Here the thermal reactor and heater are taken as single fitting stream reactor, where the
warm reactor shows an adiabatic Here the heat-exchanger is utilized as a cooling medium to
cool the outgoing sulfur fumes. Subsequent to coming out of the waste heat evaporator the
streams are cooled by means of a cooler
4.3.2 Heat Exchanger
The heat exchanger used in the sulfur recovery unit process is the time called the cooling
medium. The main purpose of using this cooling medium is to cool down the vapors of
sulphur that are coming out of the reaction furnace.
4.3.3 Separator
Another unit model that we have utilized in the sulfur recuperation unit is the separator
the fundamental reason for utilizing a separator is to separate the fluid Sulfur for a protected
stockpiling and assortment around 98 % of the fluid sulfur is gathered in the first separator
alongside some water (1.73%). Water hydrogen and hydrogen sulfide and a few hints of
methane has been gathered as fumes from the top.
4.3.4 Conversion Reactor as Catalytic Reactor:
The catalytic reactors contain expensive catalyst that improves the sulfur recuperation
proficiency with a few phase synergist units. The proficiency of the sulfur recuperation in the
adjusted provision area was 75% which was higher than 63% of the customary warm
segment. This builds the sulfur recuperation to 12% with the changed thermal segment that
happened because of the expulsion of water fumes that supported the balance-related
statement responses to happen toward sulfur creation.

34
4.4 ASSUMPTIONS
In order to simulate following assumptions are taken in the process;
1) The process is steady-state
2) We used a heat exchanger as a condenser
3) Side reaction are neglected
4) Conversion reactor is used as a catalytic reactor
5) The conversion of H₂S in the catalytic reactor is 45%.
6) The conversion reactor is CSTR

35
 CHAPTER 05
MATERIAL & ENERGY BALANCES

5.1 MATERIAL BALANCE

5.1.1 Reaction Furnace

Figure 5.1: Reaction Furnace

Reaction 1: H₂S + 1.5 O₂ → SO₂ + H₂O

Reaction 2: 2 H₂S + SO₂ → 1.5 S₂ + 2 H₂O
The conversion taken for reaction-1 is 25% and for reaction-2 is 30%. The equation for
material balance is;
Inlet – Outlet + Generation – Consumption = Accumulation ………………..…Equation-5.1
For steady state, Accumulation = 0
So,
Inlet + Generation – Consumption = Outlet……………................................……Equation 5.2

36
 Table 5.1: Molar Flowrate Calculation
Components Inlet (Kmol/h) Reaction Outlet (Kmol/h)
H₂O 19.03201635 18.856317 37.88833298
Hydrogen 0.160245235 - 0.160245235
H₂S 39.69750869 18.856317 20.84119206
Methane 0.06 - 0.06
Ethylene 0.06 - 0.06
Ethane 0.03 - 0.03
Propane 0.03 - 0.03
Nitrogen 217.1615954 - 217.1615954
Oxygen 57.56090481 14.886566 42.67433905
S2_Vapor 0 6.6989546 6.698954592
S8_Vapor 0 0 0
SO₂ 0 5.4584074 5.458407445
TOTAL 333.7855086 - 331.0563049

37
 Table 5.2: Error Calculation
Components Mole Balance Simulated
Results Results
H₂O 37.88833298 37.88833298
Hydrogen 0.160245235 0.160245235
H₂S 20.84119206 20.84
Methane 0.06 0.06
Ethylene 0.06 0.06
Ethane 0.03 0.03
Propane 0.03 0.03
Nitrogen 217.1615954 217.1615954
Oxygen 42.67433905 42.67433905
S2_Vapor 6.698954592 6.70
S8_Vapor 0 0
SO₂ 5.458407445 5.458407445
TOTAL 331.0563049 331.0563049
ERROR 0%

38
5.1.2 First Catalytic Reactor

Figure 5.2: First Catalytic Reactor

Reaction: 2 H₂S + SO₂ → 0.375 S₈ + 2 H₂O

The conversion taken for the reaction is 45%. And the (Equation-5.2) will be used for the
calculation of material balance.

39
 Table 5.3: Molar Flowrate Calculation
Components Inlet (Kmol/h) Reaction Outlet (Kmol/h)
H₂O 37.88833298 9.3785364 47.26686941
Hydrogen 0.160245235 - 0.160245235
H₂S 20.84119206 9.3785364 11.46265564
Methane 0.06 - 0.06
Ethylene 0.06 - 0.06
Ethane 0.03 - 0.03
Propane 0.03 - 0.03
Nitrogen 217.1615954 - 217.1615954
Oxygen 42.67433905 - 42.67433905
S2_Vapor 6.698954592 - 6.698954592
S8_Vapor 0 1.7584756 1.75847558
SO₂ 5.458407445 4.6892682 0.769139231
TOTAL 331.0563049 - 328.1255123

40
 Table 5.4: Error Calculation
Components Mole Balance Simulated
Results Results
H₂O 47.26686941 47.26686941
Hydrogen 0.160245235 0.160245235
H₂S 11.46265564 11.46265564
Methane 0.06 0.06
Ethylene 0.06 0.06
Ethane 0.03 0.03
Propane 0.03 0.03
Nitrogen 217.1615954 217.1615954
Oxygen 42.67433905 42.67433905
S2_Vapor 6.698954592 6.698954592
S8_Vapor 1.75847558 1.75847558
SO₂ 0.769139231 0.769139231
TOTAL 328.1255123 328.1255123
ERROR 0%

41
5.2 ENERGY BALANCE
Energy balance is used to determine the amount of energy that flows into or out of the system
that must be added or removed. It helps in assessing ways of reducing energy in order to
increase the profitability of the process. The energy balance for the sulphur recovery unit is
as follows:

Amount of Amount of Amount of Amount of

emergy energy energy energy
entering leaving generated consumed
− + −
the system the system within the within the
through through system system
[the boundaries] [ boundaries] [boundaries] [ boundaries]
Amount of
energy
accumulated
=
within the
system
[ boundaries ]
The chemical reaction taking place in the process is
Main Reaction:
3
1- 𝐻2𝑆 + 2 02 → 𝑆𝑂2 + 𝐻20 ∆𝐻 = −9833𝐾𝐽/𝐾𝑔𝑚𝑜𝑙
3
2 − 𝑆𝑂2 + 2𝐻2𝑆 → 8 𝑆8 + 2𝐻20 ∆𝐻 = −23640 𝐾𝐽/𝐾𝑔𝑚𝑜𝑙)

42
 Table 5.5: Names of streams

STREAM NO NAME IN SIMULATION

Stream-01 Acid gas
Stream-02 To reaction furnace
Stream-03 Process Air
Stream-04 To condenser-1
Stream-05 To reheater-1
Stream-06 To reheater1
Stream-07 To first catalytic reactor
Stream-08 To condenser-2
Stream-09 To reheater-2
Stream-10 To reheater-2
Stream-11 To second catalytic reactor
Stream-12 To second catalytic reactor
Stream-13 Feed to condenser
Stream-14 Liq product 3
Stream-15 Product
Stream-16 Product

5.2.1 Overall Energy Balance

43
TABLE 5.6:ENERGY BALANCE ON STREAM-1 TABLE 5.7:ENERGY BALANCE ON STREAM-1
Stream-1 -1467396 KJ/hr
Stream_03 Process air
mol Heat flow
Mol Heat flow
H2O 0.0763 -111962
H2O 0.0541 -154516
H2 0.0037 -5429.36
N2 0.7477 -2135521
H2S 0.9161 -1344281
O2 0.1982 -566083 CH4 0.0015 -2201.09
Total -2856120 C2H4 0.0013 -1907.61
KJ/hr C2H6 0.0006 -880.437
C3H8 0.0006 -880.437
TABLE 5.8:ENERGY BALANCE
ON STREAM-14
Stream-14 251466.4 KJ/hr Total -1467542
Liquid mol Heat
flow
H2O 0.0073 1835.705
H2S 0.0001 25.14664
S2 0.7603 191189.9
S8 0.2323 58415.64

Total 251466.4

44
TABLE 5.9:ENERGY BALANCE ON
STREAM-15
Stream-15 -10909328 KJ/h
TABLE 5.10:ENERGY
Mol Q(KJ/hr) BALANCE ON STREAM-16
H20 0.1525 -1663673 Stream-16 35362.29 KJ/hr
H2 0.0005 -5454.664 Liquid mol Q(KJ/hr)
H2S 0.0311 -339280.1 H2O 0.0577 2040.404
CH4 0.0002 -2181.866 H2S 0.0001 3.536229
C2H4 0.0002 -2181.866 S2 0.7216 25517.43
C2H6 0.0001 -1090.933 S8 0.2205 7797.384
C3H8 0.0001 -1090.933
N2 0.6813 -7432525 Total 35358.75
O2 0.1399 -1526215
S2 0.0001 -1090.933

Total -10974784

5.2.2 Energy Balance On Burner

TABLE 5.11 ENERGY

BALANCE ON BURNER INLET
Stream-1 -1467396 KJ/hr TABLE 5.12:ENERGY BALANCR
ONBURNER OUTLET
mol Heat flow
Stream_2 718508.6 KJ/hr
H2O 0.0763 -111962
mol(%) Q (KJ/hr)
H2 0.0037 -5429.36
H20 0.0763 54822.2
H2S 0.9161 -1344281
H2 0.0037 2658.482
CH4 0.0015 -2201.09
H2S 0.9161 658225.7
C2H4 0.0013 -1907.61
CH4 0.0015 1077.763
C2H6 0.0006 -880.437
C2H4 0.0013 934.0611
C3H8 0.0006 -880.437
C2H6 0.0006 431.1051
C3H8 0.0006 431.1051
Total 718580.4
Total -1467542

45
5.2.3 Energy Balance On Furnace

TABLE 5.13:ENERGY BALANCE

ON STREAM-O2 (FURNACE
INLET-ACID GAS)
TABLE 5.14: ENERGY BALANCE ON
Stream_2 718508.6 KJ/hr STREAM-03(PROCESS AIR)
mol(%) Q (KJ/hr) Stream_03 Process air
H20 0.0763 54822.2 mol Heat flow
H2 0.0037 2658.482
H2O 0.0541 -154516
H2S 0.9161 658225.7
N2 0.7477 -2135521
CH4 0.0015 1077.763
O2 0.1982 -566083
C2H4 0.0013 934.0611
Total -2856120
C2H6 0.0006 431.1051
C3H8 0.0006 431.1051 KJ/hr
Total 718580.4

46
TABLE 5.15 ENERGY BALANCE ON STREAM-4
(THERMAL REACTOR OUTLET)

Stream_4 -2137592 KJ/h

mol Q (KJ/h)
H20 0.1144 -244541
H2 0.0005 -1068.8
H2S 0.063 -134668
CH2 0.0002 -427.518
C2H6 0.0002 -427.518
C3H8 0.0001 -213.759
N2 0.656 -1402261
O2 0.1289 -275536
S2 0.0202 -43179.4
SO2 0.0165 -35270.3
Total -2102322

5.2.4 Energy Balance On Condenser-01

47
TABLE 5.16:ENERGY
BALANCE ON BURNER TABLE 5.17:ENERGY BALANCE ON
OUTLET (VAPOUR) CONDENSER OUTLET (LIQUID)
Stream_5 -9587830 KJ/h Stream_6 284059.3 KJ/h
Mol Q (KJ/h) mol Q (KJ/h)
H2O 0.1164 -1116023 H2O (L) 0.017 4829.008
H2 0.0005 -4793.92 H2S (L) 0.0002 56.81185
H2S 0.0642 -615539 S2(L) 0.9827 279145
CH4 0.0002 -1917.57 SO2 (L) 0.0001 28.40593
C2H4 0.0002 -1917.57 Total 284059.3
C2H6 0.0001 -958.783
C3H8 0.0001 -958.783
N2 0.6691 -6415217
O2 0.1315 -1260800 TABLE 5.18:ENERGY BALANCE ON
S2 0.0009 -8629.05 STREAM-4
SO2 0.0168 -161076 Stream_4 -2137592 KJ/h
Total -9426755 Mol Q (KJ/h)
H20 0.1144 -244541
H2 0.0005 -1068.8
H2S 0.063 -134668
CH2 0.0002 -427.518
C2H6 0.0002 -427.518
C3H8 0.0001 -213.759
N2 0.656 -1402261
O2 0.1289 -275536
S2 0.0202 -43179.4
SO2 0.0165 -35270.3
Total -2102322

48
5.2.5 Energy Balance On Reheater-01

TABLE 5.19:ENERGY BALANCE

ON REHEATER (INLET-1) TABLE 5.20:ENERGY BALANCE
ON REHEATER-01 INLET
Stream_5 -9587830 KJ/h (STREAM-06)
mol Q (KJ/h) Stream_6 284059.3 KJ/h
H2O 0.1164 -1116023 Mol Q (KJ/h)
H2 0.0005 -4793.92 H2O (L) 0.017 4829.008
H2S 0.0642 -615539 H2S (L) 0.0002 56.81185
CH4 0.0002 -1917.57 S2(L) 0.9827 279145
C2H4 0.0002 -1917.57 SO2 (L) 0.0001 28.40593
C2H6 0.0001 -958.783 Total 284059.3
C3H8 0.0001 -958.783
N2 0.6691 -6415217
TABLE 5.21:ENERGY BALANCE
O2 0.1315 -1260800
ON REHEATER OUTLET
S2 0.0009 -8629.05
Stream_7 -7604701 KJ/h
SO2 0.0168 -161076
mol Q(KJ/h)
Total -9426755
H2O 0.1144 -869978
H2 0.0005 -3802.35
H2S 0.063 -479096
CH4 0.0002 -1520.94
C2H4 0.0002 -1520.94
C2H6 0.0001 -760.47
C3H8 0.0001 -760.47
N2 0.656 -4988684
49
 O2 0.1289 -980246
S2 0.0202 -153615
SO2 0.0165 -125478
Total -7605462

5.2.6 Energy Balance On Catalytic Reactor-01

TABLE 5.23:ENERGY BALANCE

TABLE 5.22:ENERGY BALANCE ON REACTOR-01 OUTLET
ON REACTOR-01 INLET Stream-8 -7604701 KJ/h
Stream_7 -7604701 KJ/h mol Q(KJ/h)
mol Q(KJ/h) H2O 0.1141 -867696
H2O 0.1144 -869978 H2 0.0005 -3802.35
H2 0.0005 -3802.35 H2S 0.0349 -265404
H2S 0.063 -479096 CH4 0.0002 -1520.94
CH4 0.0002 -1520.94 C2H4 0.0002 -1520.94
C2H4 0.0002 -1520.94 C2H6 0.0001 -760.47
C2H6 0.0001 -760.47 C3H8 0.0001 -760.47
C3H8 0.0001 -760.47 N2 0.6618 -5032791
N2 0.656 -4988684 O2 0.1301 -989372
O2 0.1289 -980246 S2 0.0204 -155136
S2 0.0202 -153615 S8 0.0054 -41065.4
SO2 0.0165 -125478 SO2 0.0023 -17490.8
Total -7605462 Total -7377321

50
5.2.7 Energy Balance On Condenser-02

TABLE 5.25:ENERGY BALANCE

ON CONDENSER-02 OUTLET(L)
Stream-9 -10375446 KJ/h
mol Q(KJ/h)
H2O 0.1472 -1527266
H2 0.0005 -5187.723
H2S 0.0359 -372478.5
CH4 0.0002 -2075.089
C2H4 0.0002 -2075.089
C2H6 0.0001 -1037.545
C3H8 0.0001 -1037.545
N2 0.6793 -7048041
O2 0.1335 -1385122
S2 0.0005 -5187.723
S8 0.0001 -1037.545
51
 SO2 0.0024 -24901.07
Total -10375446
TABLE 5.24:ENERGY
BALANCE ON CONDENSER-2
INLET
Stream-8 -7604701 KJ/h
mol Q(KJ/h)
H2O 0.1141 -867696
H2 0.0005 -3802.35
H2S 0.0349 -265404
CH4 0.0002 -1520.94
C2H4 0.0002 -1520.94
C2H6 0.0001 -760.47
C3H8 0.0001 -760.47
N2 0.6618 -5032791
O2 0.1301 -989372
S2 0.0204 -155136
S8 0.0054 -41065.4
SO2 0.0023 -17490.8
Total -7377321

TABLE 5.26:ENERGY BALANCE

ON CONDENSER-2 OUTLET (V)
Stream-10 249623.3 KJ/h
mol Q(KJ/h)
H2O 0.0243 6065.846
H2S 0.0001 24.96233
S2 0.7727 192883.9
S8 0.2028 50623.61

Total 249598.3

5.2.8 Energy Balance On Reheater_02

52
TABLE 5.27:ENERGY BALANCE
ON STREAM-09 TABLE 5.28:ENERGY
Stream-9 -10375446 KJ/h BALANCE ON STREAM-10
mol Q(KJ/h) Stream-10 249623.3 KJ/h
H2O 0.1472 -1527266 mol Q(KJ/h)
H2 0.0005 -5187.723 H2O 0.0243 6065.846
H2S 0.0359 -372478.5 H2S 0.0001 24.96233
CH4 0.0002 -2075.089 S2 0.7727 192883.9
C2H4 0.0002 -2075.089 S8 0.2028 50623.61
C2H6 0.0001 -1037.545
C3H8 0.0001 -1037.545 Total 249598.3
N2 0.6793 -7048041
O2 0.1335 -1385122
S2 0.0005 -5187.723
S8 0.0001 -1037.545
SO2 0.0024 -24901.07
Total -10375446

TABLE 5.29:ENERGY BALANCE

ON STREAM-11
Stream-11 -9677491 KJ/h

Vapor mol Heat flow

H2O 0.1496 -1447753
H2 0.0005 -4838.75
H2S 0.0357 -345486
CH4 0.0002 -1935.5
C2H4 0.0002 -1935.5
C2H6 0.0001 -967.749
C3H8 0.0001 -967.749
53
 TABLE 5.30:ENERGY
BALANCE ON STREAM-12
Stream-12 262845.7 KJ/hr
Liquid mol Heat
flow
N2 0.6755 -6537145 H2O 0.008 2102.766
O2 0.1327 -1284203 H2S 0.0001 26.28457
S2 0.00046 -4451.65 S2 0.7856 206491.6
S8 0.0012 -11613 S8 0.2062 54198.78
SO2 0.0024 -23226
Total 262819.4
Total -9664524

5.2.9 Energy Balance On Second Catalytic Reactor

TABLE 5.31:ENERGY BALANCE

ON REACTOR-2 INLET
Stream-11 -9677491 KJ/h

54
 TABLE 5.32:ENERGY
TABLE 5.35:ENERGY
BALANCE ON REACTOR 2
Vapor mol Heat flow
BALANCE ON CONDENSER-3
INLET(STREAM-12)
H2O 0.1496 -1447753
H2 0.0005 -4838.75 Stream-12 262845.7 KJ/hr
H2S 0.0357 -345486 Liquid mol Heat
flow
CH4 0.0002 -1935.5
H2O 0.008 2102.766
C2H4 0.0002 -1935.5
H2S 0.0001 26.28457
C2H6 0.0001 -967.749
S2 0.7856 206491.6
C3H8 0.0001 -967.749
S8 0.2062 54198.78
N2 0.6755 -6537145
Total 262819.4
O2 0.1327 -1284203
S2 0.00046 -4451.65
S8 0.0012 -11613
SO2 0.0024 -23226 TABLE 5.34:ENERGY
BALANCE ON STREAM-14
Total -9664524 Stream-14 251466.4 KJ/hr
Liquid mol Heat
flow
H2O 0.0073 1835.705
H2S 0.0001 25.14664
S2 0.7603 191189.9
S8 0.2323 58415.64
Total 251466.4
TABLE 5.33:ENERGY BALANCE
ON STREAM-13
Stream-13 -9666046 KJ/h
Vapour mol Heat flow
H2O 0.1518 -1467306
H2 0.0005 -4833.02
H2S 0.0309 -298681
CH4 0.0002 -1933.21
C2H4 0.0002 -1933.21
C2H6 0.0001 -966.605
C3H8 0.0001 -966.605
N2 0.676 -6534247
O2 0.1328 -1283651
S2 0.0057 -55096.5
S8 0.0017 -16432.3
Total -9666046

55
 INLET (STREAM-13)
Stream-13 -9666046 KJ/h
Vapour mol Heat flow
H2O 0.1518 -1467306
H2 0.0005 -4833.02
H2S 0.0309 -298681
CH4 0.0002 -1933.21
C2H4 0.0002 -1933.21
C2H6 0.0001 -966.605
C3H8 0.0001 -966.605
N2 0.676 -6534247
O2 0.1328 -1283651
S2 0.0057 -55096.5
S8 0.0017 -16432.3
Total -9666046

5.2.10 Energy Balance On Condenser-03

TABLE 5.36:ENERGY BALANCE

ON CONDENSER-3 INLET
(STREAM-14)
Stream-14 251466.4 KJ/hr
Liquid mol Heat flow
H2O 0.0073 1835.705
H2S 0.0001 25.14664
S2 0.7603 191189.9
S8 0.2323 58415.64
Total 251466.4

56
 TABLE 5.37:ENERGY BALANCE ON
CONDENSER-3 OUTLET(STREAM-15)
Stream-15 -10909328 KJ/h
mol Q(KJ/hr)
H20 0.1525 -1663673
H2 0.0005 -5454.664
H2S 0.0311 -339280.1
CH4 0.0002 -2181.866
C2H4 0.0002 -2181.866
C2H6 0.0001 -1090.933
C3H8 0.0001 -1090.933
N2 0.6813 -7432525
O2 0.1399 -1526215
S2 0.0001 -1090.933

Total -10974784

TABLE 5.38:ENERGY BALANCE ON

REACTOR-3 OUTLET(STREAM-16)
Stream-16 35362.29 KJ/hr
Liquid mol Q(KJ/hr)
H2O 0.0577 2040.404
H2S 0.0001 3.536229
S2 0.7216 25517.43
S8 0.2205 7797.384

Total 35358.75

57
 REFERENCES

[1] B. MEYER, "ELEMENTAL SULFUR," p. 76, 4 MARCH 1975.

[2] LINKER, "GlobeNewswire," Reportlinker, 15 JULY 2020. [Online]. Available:

https://www.globenewswire.com/news-release/2020/07/15/2062351/0/en/Global-Sulfur-
Sulphur-Industry.html.

[3] MAPS, "Maps of World," 12 DECEMBER 2012. [Online]. Available:

https://www.mapsofworld.com/minerals/world-sulphur-producers.html.

[4] S. Amirie, "the sulfur institue," [Online]. Available: https://www.sulphurinstitute.org/about-

sulphur/sulphur-the-fourth-major-plant-nutrient/sulphur-fertilizer-types/elemental-sulphur/.

[5] "ENVIRONMENTAL PROTECTION AGENCY," [Online]. Available:

https://www.epa.gov/acidrain/what-acid-rain.

[6] D. Duissenov, "Production and processing of sour crude".

[7] S. M. James, "Calgary First Aid," [Online]. Available: https://bit.ly/2WAPKlw.

[8] "Hydrogen Sulfide (H2S," [Online]. Available: http://bit.ly/37JgCGc.

[9] E.Goldsmith, "Hydrogen sulphide, its uses and dangers".

[10] SCEINCING, "Uses for Hydrogen Sulfide," [Online]. Available: https://bit.ly/2KPkwog.

[11] A. I. T. S. b. Country, "TrendEconomy," 18 2 2021. [Online]. Available: http://bit.ly/3aiO5ZR.

[12] A. kohl, "GAS PURIFICATION," 1997.

[13] J. A. DUTTON, "Petroleum Processing," [Online]. Available: https://www.e-

education.psu.edu/fsc432/content/modified-claus-process.

[14] I. MARKIT, "Chemical Economics Handbook," DECEMBER 2020. [Online]. Available:

https://ihsmarkit.com/products/sulfur-chemical-economics-handbook.html.

[15] "Sulfur Recovery Process," [Online]. Available: https://www.sulfurrecovery.com/sru-from-a-to-

z.

[16] S. Bandyopadhyay, "Design of Heat Recovery Equipments in Sulfur Recovery Unit".

[17] linde, "linde group sulfur recovery process," linde group , [Online]. Available:
https://www.linde-engineering.com/en/images/Sulfur%20Process%20Technology_tcm19-
111155.pdf.

58
59