Clean Synthesis of Adipic Acid from

Cyclohexene using Hydroperoxide as a

Catalyst

Submitted by:

M. Osama Khalid 2016-CH-21

Atif Ishfaq 2016-CH-40
Takreem Ahmad Sindhu 2016-CH-55
Faiza Quadoom Raja 2016-CH-59

Supervised by: Dr. H. M. Zaheer

Year: 2016
 Department of Chemical Engineering
University of Engineering and Technology Lahore
The thesis titled “Clean synthesis of adipic acid from cyclohexene using hydrogen peroxide as a
catalyst” is being submitted to the Department of Chemical Engineering, University of Engineering and
Technology Lahore in partial fulfillment of the requirement for the Degree of

Bachelor of Science in Chemical Engineering

Internal Examiner External Examiner

Chairman
Department of Chemical Engineering

Department of Chemical Engineering

University of Engineering and Technology Lahore

ii
 Declaration
I declare that the work contained in this thesis is my own, except where explicitly stated
otherwise. In addition this work has not been submitted to obtain another degree or
professional qualification.

Signature:

Date:

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 Acknowledgments
First and foremost, praises and thanks to the ALLAH, the Almighty, for His showers

of blessings throughout to complete our final year project successfully.

We would like to express our deep and sincere gratitude to our project supervisor, Dr.

Hafiz M. Zaheer Aslam, for giving us the opportunity to do our project and providing

invaluable guidance throughout the period of research. His dynamism, vision, sincerity

and motivation have deeply inspired us. He has taught us the methodology to carry out

the project and to present the works as clearly as possible. It was a great privilege and

honor to work and study under his guidance. I am extremely grateful for what he has

offered me.

We are thankful to our teachers for their shear guidance and cooperation. In the end, we are

thankful to our parents for being there for us throughout our educational career.

Our Special thanks goes to our friends and peers for their keen interest shown to complete

this thesis successfully.

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Dedicated to the Creator, the ultimate source of
inspiration, strength, knowledge and understanding,
against who’s will nothing is possible. Also dedicated to
our beloved parents and teachers who have been
affected in every way possible by this quest.

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Contents :
Abstract ...................................................................................................................................... 1
1. Introduction ....................................................................................................................... 2
1.2. Introduction of Adipic Acid ........................................................................................ 2
1.3. History ......................................................................................................................... 2
1.4. Physical Properties ...................................................................................................... 2
1.5. Chemical Properties: ................................................................................................... 3
1.6. Industrial Applications ................................................................................................ 3
1.6.1. Precursor for Nylon: ................................................................................................ 3
1.6.2. Pharmaceutical Industries: ....................................................................................... 3
1.6.3. In Foods: .................................................................................................................. 3
1.7. Quality Specifications ................................................................................................. 3
1.8. Storage and Transportation ......................................................................................... 4
1.9. Market Survey ............................................................................................................. 4
1.9.1. Domestic and Global Market Analysis of Adipic Acid:.......................................... 4
1.9.2. Global Market: ......................................................................................................... 5
1.9.3. Leading Producers in the World .............................................................................. 7
2. Process Selection and Description ................................................................................... 8
2.1. Process Selection: ........................................................................................................ 8
2.1.1. Synthesis of Adipic Acid Via The Nitric Acid Oxidation of Cyclohexanol in a
Two Step Batch Process: ..................................................................................................... 8
2.1.2. Green Catalytic Oxidation of Cyclohexanone to Adipic Acid ................................ 9
2.1.3. Influence of Reaction Conditions on Product distribution of Cyclohexene to
Adipic Acid from H2O2 ...................................................................................................... 9
2.1.4. Dual catalytic function of the task specific ionic liquid. Green oxidation of
Cyclohexene to Adipic Acid using 30% H2O2 .................................................................. 9
2.1.5. Hydrothermal synthesis of WO3 nano rods and their performance in the
adsorption of Rhodamine .................................................................................................... 9
2.1.6. Dawson-type polyoxometalates as Green catalyst for Adipic Acid synthesis ........ 9
2.2. Process Description: .................................................................................................. 10
2.3. Process Flow diagram: .............................................................................................. 11
3. Material and Energy Balance......................................................................................... 12
3.1. MATERIAL BALANCE ....................................................................................... 12
3.1.1. Capacity of Plant: .................................................................................................. 12
3.2. Energy Balance ......................................................................................................... 15
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 1.1 For steady state system no accumulation of mass or energy with in system, so by
modifying above equation, and applying across each equipment, the energy balance of
each equipment is as under. .................................................................................................. 15
3.2.1. Around heat exchanger#1:..................................................................................... 15
3.2.2. Around heat exchanger 2: ...................................................................................... 15
3.2.3. Around Chemical Reactor ..................................................................................... 15
3.2.4. Around heat exchanger 3: ...................................................................................... 16
3.2.5. Around crystallizer#1: ........................................................................................... 16
3.2.6. Around heat exchanger #4: .................................................................................... 16
3.2.7. Around Evaporator: ............................................................................................... 17
3.2.8. Around heat exchanger# 5: .................................................................................... 17
3.2.9. Around crystallizer#2: ........................................................................................... 18
3.2.10. Around heat exchanger # 6 ................................................................................ 18
3.2.11. Around Dryer: .................................................................................................... 18
4. Detailed Equipment Design ............................................................................................ 20
4.1. Reactor: ..................................................................................................................... 20
4.1.1. Types of reactor: .................................................................................................... 20
4.1.2. Continuously Stirred Tank Reactor and its Operation: ......................................... 22
4.1.3. Known Parameters and Assumptions: ................................................................... 22
4.1.4. Design calculations: ............................................................................................... 23
4.1.5. Specification sheet of reactor: ............................................................................... 24
4.2. Crystallizer ................................................................................................................ 25
4.2.1. Types of Continuous Crystallizers ........................................................................ 25
4.2.2. Selection: ............................................................................................................... 25
4.2.5. Design Specifications Sheet .................................................................................. 28
4.3. Separator: .................................................................................................................. 28
4.3.1. Objective:............................................................................................................... 28
4.3.2. Description: ........................................................................................................... 28
4.3.3. Significance in Process .......................................................................................... 28
4.3.4. 2-phase horizontal Separator ................................................................................. 29
4.3.5. Design of Separator: .............................................................................................. 30
4.3.6. Design Specification Sheet: ................................................................................... 31
4.4. Evaporator ................................................................................................................. 31
4.4.1. Types of Evaporator .............................................................................................. 31
4.4.2. Selection Criteria ................................................................................................... 32
4.4.3. Long Tube Falling-Film Evaporator...................................................................... 32
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 4.4.4. Number of Effects ................................................................................................. 33
4.4.5. Design Steps .......................................................................................................... 33
4.4.6. Assumptions and Fluid Allocation ........................................................................ 34
4.4.7. Design Overall Heat Transfer Coefficient ............................................................. 35
4.4.8. Design Specifications Sheet .................................................................................. 37
4.5. Dryer: ........................................................................................................................ 37
4.5.1. Objective:............................................................................................................... 37
4.5.2. Description: ........................................................................................................... 37
4.5.3. Significance in Process .......................................................................................... 37
4.5.4. Rotary dryer ........................................................................................................... 38
4.5.5. Design of Separator: .............................................................................................. 38
4.5.6. Design Specification Sheet: ................................................................................... 40
4.6. Heat Exchanger ......................................................................................................... 40
4.6.1. Types: .................................................................................................................... 40
4.6.1.1. Parallel flow heat exchanger .............................................................................. 40
4.6.1.3. Counter flow heat exchanger: ................................................................................ 41
4.6.1.4. Finned tubular heat exchanger:.............................................................................. 41
4.6.1.5. Un-finned tubular heat exchanger: ........................................................................ 42
4.6.1.6. Micro channel heat exchanger: .............................................................................. 42
4.6.1.7. Shell and tube type heat exchanger: ...................................................................... 42
4.6.1.8. u-tube single and 2 pass heat exchanger:............................................................... 42
4.6.1.9. Double pipe heat exchanger: ................................................................................. 42
4.6.1.10. Plate type heat exchanger: ................................................................................. 42
4.6.1.11. Selected Heat Exchanger ................................................................................... 43
4.6.2. Known parameters and assumptions: ........................................................................ 43
4.6.3. HYSYS Simulation: .............................................................................................. 44
4.6.4. Design Specification Sheet: ................................................................................... 45
4.7. Decanter: ................................................................................................................... 45
4.7.1. Types ..................................................................................................................... 46
4.7.2. Design equipment criteria ...................................................................................... 47
Adipic acid ............................................................................................................................ 47
Water .................................................................................................................................... 47
4.7.3. Piping arrangement ................................................................................................ 48
4.7.4. Design Specification Sheet: ................................................................................... 49
5. INSTRUMENTATION AND CONTROL ...................................................................... 50
5.1. Introduction: .............................................................................................................. 50
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 5.2. Incentives for chemical process control: ................................................................... 50
5.3. Classification of variables in chemical process: ....................................................... 51
5.3.1. Manipulated Variables:.......................................................................................... 51
5.3.2. Loads or Disturbances: .......................................................................................... 51
5.3.3. Hardware for a process control element: ............................................................... 51
6. HAZOP Analysis ............................................................................................................. 53
6.1. HAZOP Introduction: ................................................................................................ 53
6.2. Objectives of HAZOP: .............................................................................................. 53
6.3. HAZOP Analysis methodology: ............................................................................... 53
6.4. Terms used in HAZOP study: ................................................................................... 54
6.5. Guide words: ............................................................................................................. 55
6.6. HAZOP analysis of Heat exchanger: ........................................................................ 55
7. Cost Estimation ............................................................................................................... 57
7.1. Purchased Equipment Cost ....................................................................................... 57
7.2. Total Capital Investment: .......................................................................................... 57
7.2.1. Fixed Capital Investment: ....................................................................................... 57
7.3. Total Production Cost................................................................................................ 59
7.3.1. Variable Cost ........................................................................................................... 59
7.3.2. Fixed Cost ............................................................................................................. 60
7.3.3. Overhead Charges: ................................................................................................ 60
7.4. Production Cost ......................................................................................................... 60
References: ............................................................................................................................... 61

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List of Figures
Figure 1: Global Adipic Acid Market Share .............................................................................. 5
Figure 2: India Adipic Acid in PU market ................................................................................. 6
Figure 3:U.S. Adipic Acid market ............................................................................................. 6
Figure 4: Process Flow Diagram.............................................................................................. 11
Figure 5: continuously stirred tank reactor .............................................................................. 21
Figure 6: graph for time vs conversion .................................................................................... 23
Figure 7:Long tube falling film evaporator ............................................................................ 32
Figure 8:Constants to be used in correlation............................................................................ 35
Figure 9:Shell Clearance .......................................................................................................... 35
Figure 10: HYSYS results of performance indicators on Heat Exchanger ............................. 44
Figure 11: HYSYS results of streams ...................................................................................... 44

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List of Tables
Table 1: Properties of Adipic Acid ............................................................................................ 3
Table 2: Quality Specification of adipic Acid ........................................................................... 4
Table 3:Material Balance around reactor ................................................................................. 12
Table 4:Material Balance around Decanter ............................................................................. 12
Table 5: Material Balance around crystallizer 1 ...................................................................... 13
Table 6: Material Balance around filter 1 ................................................................................ 13
Table 7:Material balance around evaporator ........................................................................... 13
Table 8: Material balance around crystallizer 2 ....................................................................... 14
Table 9: Material balance around filter 2 ................................................................................. 14
Table 10: material balance around dryer ................................................................................. 14
Table 11:Specification Sheet of Reactor.................................................................................. 24
Table 12:thermophysical properties ......................................................................................... 26
Table 13:Specification sheet of Crystallizer ............................................................................ 28
Table 14: comparison of different separators .......................................................................... 29
Table 15: Specification sheet of separator ............................................................................... 31
Table 16: thermo-physical properties ...................................................................................... 33
Table17 :specification sheet of Evaporator.............................................................................. 37
Table 18: Comparison of Different types of separators ........................................................... 38
Table 19: Specification Sheet of Dryer .................................................................................... 40
Table 20: Specification Sheet of Heat exchanger .................................................................... 45
Table 21: Specification Sheet of Decanter............................................................................... 49
Table 22:Purchased Equipment cost ........................................................................................ 57
Table 23: Direct Cost ............................................................................................................... 58
Table 24: Indirect Cost............................................................................................................. 58
Table 25: Miscellaneous .......................................................................................................... 59
Table 26: fixed cost .................................................................................................................. 60

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Abstract

The adipic acid is mainly used for the production of nylon, industrially important as raw
material for the textile industry. For the process to be clean and environmental friendly, the
chemicals Like H202 as an oxidant and sodium tungstate as a catalyst were used instead of
HNO3 due to emission of N2O gas which is one of the hazardous gas for environment.
Different parameters like molar ratio of catalyst and reactants, concentration of hydrogen per
oxide, molarity of acid, temperature, and residence time were optimized to obtain high yield
of adipic acid. Cyclohexanone is oxidized to adipic acid and water produced as the main by-
product. The units which we designed includes a heat exchanger, reactor, decanter,
crystallizer, separator and dryer. HAZOP study was conducted on the heat exchanger.
Economic feasibility, efficiency and operability were the basis for the design of the units
mentioned above. In the end, we estimated the capital cost for the production process and
discussed its profitability.

1
Chapter 1

1. Introduction
This chapter provides an introduction to adipic acid with its history and properties. Industrial
Applications, Storage and Safety. Finally, a market survey is provided at the end of the
chapter.
1.2. Introduction of Adipic Acid
Adipic acid is a straight-chain dicarboxylic acid that is similar to a white crystalline
compound at standard temperature and pressure. Adipic acid is one of the most important
industrial chemicals and is usually in the top 10 in quantities used by the chemical industry. It
is very rare in nature, but is made mostly around the world. Its primary application is in the
production of nylon 66 polyamide.
1.3. History
Adipic acid is found in beet juice. In 1906, the French chemist L. Bawalt and R. Loquin
claimed that cyclohexanol can be oxidized to produce fatty acids. W. H. Carolus of DuPont
invented the nylon 66 polyamide in the early 1930s. Nylon 66 polyamide fibers have become
a major process in the synthetic fiber industry, leading to the development of adipic acid. In
1940, DuPont developed a commercial method for producing adipic acid using crude oil from
benzene, but it has been modified over the years. The historical development of adipic acid
was reviewed in 1977.
1.4. Physical Properties
Adipic acid is separated into a colorless, odorless crystal with an acid taste. It is highly
soluble in methanol and ethanol, soluble in water and acetone, and slightly soluble in
cyclohexane and benzene. Adipic acid crystallizes from water, ethyl acetate or acetone /
petroleum ether as a monoclinic prism. Some physical properties of Adipic Acid are:

Properties Values

Molecular Weight 146.14 g/mol

Boiling Point 337.5 ℃

Melting Point 151.11 ℃

Density at 25℃ 1360 Kg/m3

Vapor Pressure at 25℃ 3.02*10-5 Pa

Viscosity of Melt at 160℃ 0.00454

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Heat of Combustion -2800 KJ/mol

Heat of Vaporization 549 KJ/Kg

Auto-ignition Temperature 420℃

Flash Point 196℃

Table 1: Properties of Adipic Acid

1.5. Chemical Properties:

Adipic acid is stable in air under most conditions, but some decarboxylation takes place by
heating more than 230 - 250℃ results cyclopentanone. The reaction is clearly catalyzed by
the salts of metals including iron, calcium and barium. The tendency of adipic acid to form
cyclic anhydride from water loss is much lower than that of glutaric or succinic acid. Adipic
acid reacts readily to one or two carboxylic acid groups to form salts, esters, amides, nitriles,
etc. As is evident from its production in nitric acid, the acid is very stable for many oxidizing
agents. However, nitric acid automatically attacks adipic acid above 180℃, producing carbon
dioxide, water and nitrogen oxide.
1.6. Industrial Applications
Major industrial applications of Adipic Acid are:
1.6.1. Precursor for Nylon:
A common use of adipic acid is as a starting material for nylon synthesis. Approximately
90% of the produced adipic acid is used in the production of nylon 66. Industrial chemists
take adipic acid and make nylon and react with hexamethylene diamine. Nylon is used in
many applications, including fiber, plastic, filament and food packaging material.
1.6.2. Pharmaceutical Industries:
Although adipic acid is not used as a therapeutic agent, its use has been found in ce ce and in
ce ce industries. Adipic acid is included in tablets to aid in the controlled release of acid and
basic drug formulations. When there is no stomach acid-like compound, the residue is
released into the body as soon as it hits the stomach. The use of adipic acid helps regulate the
release of the compound for a short period of time, which helps to avoid taking the
preservative in a short period of time.
1.6.3. In Foods:
Adipic acid is used in the food industry as a flavoring and gel. Adipic acid is sometimes used
in antacid tablets.
1.7. Quality Specifications
Commercial Adipic Acid are one of the pure mass chemicals produced by the stringent
requirements of their main customers, the synthetic fiber industry. The U.S Food and Drug

3
Administration approves adipic acid as a food additive. Because all adipic acid manufacturers
use the nitric acid oxidation process, the impurities are the same.
Some typical specifications for adipic acid are:
Mass portion of Adipic Acid, %, not less than 99.8

Color of solution (Solvent color) by platinum- 2.5

cobalt (PT-Co) scale, Hazen Units, not more than

Color of melt (Molten color) by platinum-cobalt 30

(PT-Co) scale, Hazen Units, not more than

Temperature of melt (range) ºC, minimum 152.0 (– 155.0)

Mass portion of water, %, not more than 0.18

Mass portion of ash, %, not more than 0.0015

Mass portion of nitric acid, %, not more than 0.0003

Mass portion of iron, %, not more than 0.00005

Mass portion of oxalic acid, %, not more than 0.004

Table 2: Quality Specification of adipic Acid

1.8. Storage and Transportation

Adipic acid can be transported from the drying device to a storage or shipping container,
either aerobically or mechanically. These containers can be aluminum or stainless-steel
railroad hopper cars, trucks, plastic bags or drums. The main risk of administering adipic acid
is the risk of blasting dust and irritation of the skin or mucous membranes. Particle size
control and flow characteristics are also important factors that lead to the uptake of Adipic
Acid. It is stored at a maximum temperature of 50℃.
Safety
Adipic Acid is non-hazardous and non-reactive at normal conditions.
1.9. Market Survey
1.9.1. Domestic and Global Market Analysis of Adipic Acid:
05 October 2015 - Fast-growing economies, mainly in China and India, have significantly
increased global demand for adipic acid over the past 10 years. Adipic acid production is
growing in the Asia-Pacific region as startups and small companies enter the market, BCC
Research said in a new report.

4
Figure 1: Global Adipic Acid Market Share

1.9.2. Global Market:

▪ The global market for IP Adipic Acid should reach $ 6.6 billion and $7.7 billion in
2015 and 2020, respectively, reflecting a five-year (2015-2020) compound annual
growth rate (CAGR) of 3.2%. The global adipic acid market, the largest and fastest
growing end-user application for the automotive industry, is expected to reach
approximately $2.6 billion by 2020, up from $ 2.1 billion in 2015 and a five-year
CAGR of 4.2%. The market for the electrical and electronics industry, the second
largest end-user application, should register a five-year CAGR of 2.7%, bringing the
total market value to 1 1.1 billion by 2020.
▪ And this growth is driven partly by North American and European regions. But the
Asia-Pacific region dominates the market.
▪ And adipic acid, which is used in the manufacture of nylon 66 fibers and resins, is
estimated to be about 2,600 kilo-tons in 2016. These sectors are expected to expand at
a healthy CAGR of 4.2% and 3.6%, respectively. Nylon 66 consumption for global
electronic security equipment is projected to be approximately 20.9 kilo-tons in 2015.
▪ "In the Asia-Pacific, the automotive and footwear industry is expected to grow in
China and India," says BCC Research Analyst Anish Kumar. China mainly
manufactures car parts, parts and parts for automobiles and electric motors. China's
entry into the WTO has helped the country develop automobile parts and accessories
markets. India is one of the largest footwear manufacturers and produces 3 billion
pairs every year. China and India each have a large footwear industry, which mostly
uses polyurethane. This is expected to boost the market over the next five years. "

5
 ▪ In 2016, India’s adipic acid market size was estimated at US $ 186.9 million. The
market expects a 6.2% CAGR in the forecast period.

Figure 2: India Adipic Acid in PU market

▪ Global Markets for Adipic Acid (CHM055A) examines global adipic acid use by
regions, intermediate applications and end-user applications. The report identifies the
market dynamics, growth drivers, inhibitors, opportunities and forecast trends and
revenue for 2020.
▪ The Global Adipic Acid Market size is estimated to be USD 5.56 Billion in 2016 and
is expected to grow at a CAGR of 4.7% over the forecast period.

Figure 3:U.S. Adipic Acid market

▪ North America's largest consumer market for the adipic acid market, however, APAC
is rapidly growing for adipic acid due to the huge demand from India, China and
Japan for Adipic acid in various domains such as agriculture. There is a growing
market for consumer goods and automobiles.

6
1.9.3. Leading Producers in the World
➢ Asahi Kasei Corporation (Japan)
➢ Ascend Performance Materials, LLC (USA)
➢ BASF SE (Germany)
➢ BioAmber, Inc. (Canada)
➢ Genomatica, Inc. (USA)
➢ Huafon Group Co., Ltd. (China)
➢ INVISTA (USA)
➢ JiangSu Haili Chemical Industry Co. Ltd. (China)
➢ LANXESS AG (Germany)
➢ PetroChina Company Ltd. (China)
➢ Radici Partecipazioni SpA (Italy)
➢ Shandong Haili Chemical Industry Co., Ltd. (China)
➢ Shandong Hongye Chemical Group Co., Ltd. (China)
➢ Solvay SA (Belgium)
➢ Sumitomo Shoji Chemical Co., Ltd. (Japan)
➢ Taiyuan Chemical Industry Group Co., Ltd. (China)
➢ Tokyo Chemical Industry Co., Ltd. (Japan)
➢ Verdezyne, Inc. (USA)

7
Chapter 2

2. Process Selection and Description

2.1. Process Selection:
The production of Adipic Acids world-wide have also many methods. Some of the methods
are given below:
▪ Synthesis of Adipic Acid Via The Nitric Acid Oxidation of Cyclohexanol in a Two
Step Batch Process
▪ Clean Synthesis of Adipic Acid by direct Oxidation of Cyclohexene with H2O2
▪ Green Catalytic Oxidation of Cyclohexanone to Adipic Acid
▪ Influence of Reaction Conditions on Product distribution of Cyclohexene to Adipic
Acid from H2O2
▪ Dual catalytic function of the task specific ionic liquid. Green oxidation of
Cyclohexene to Adipic Acid using 30% H2O2
▪ Hydrothermal synthesis of WO3 nano rods and their performance in the adsorption of
Rhodamine
▪ Dawson-type polyxomatalates as Green catalyst for Adipic Acid synthesis
2.1.1. Synthesis of Adipic Acid Via The Nitric Acid Oxidation of Cyclohexanol in a Two
Step Batch Process:
On industrial scale the production of Adipic Acid is occurring. The higher rate is because of
its use in making other things just like nylon6-6. One of the method is Two step Batch
Process using HNO3. The catalyst used for this process is Vanadium. Vanadium is a
chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey,
malleable transition metal. The elemental metal is rarely found in nature, but once isolated
artificially, the formation of an oxide layer (passivation) somewhat stabilizes the free metal
against further oxidation. This method has 95% yield and 22Hr residence time operated at
1atm pressure.
There are certain difficulties in this method as enlisted below:
• Vanadium is a very rare and expensive
• Using HNO3 produce N2O which cause Acid Rain
• Not a environment friendly process
• Cause ozone depletion

8
2.1.2. Green Catalytic Oxidation of Cyclohexanone to Adipic Acid
It is an environment friendly process using Hydrogen peroxide as oxidant and Tungstic Acid
(H2WO4) as a catalyst. Tungstic acid refers to hydrated forms of tungsten trioxide. It gave us
91% yield at 1 atm pressure and 90 degree C. the residence time for this process is 20Hr.
The disadvantages for not using this process are
▪ The yield is low
2.1.3. Influence of Reaction Conditions on Product distribution of Cyclohexene to Adipic
Acid from H2O2
It is one of the cheapest method for the production of Adipic Acid. The process is operated at
1 atm pressure and 80 deg C temperature. The for the process is 90.7% and the residence time
is 7Hrs.
The disadvantages for not using this process is that the yield is very low and the process is at
optimized conditions.
2.1.4. Dual catalytic function of the task specific ionic liquid. Green oxidation of
Cyclohexene to Adipic Acid using 30% H2O2
Cyclohexene is used for this process and oxidant is Hydrogen peroxide using various
catalysts. The yield for the process is 85% operated at 85 deg C temperature and 1 atm
pressure.
The disadvantages for not using this process is
▪ The reaction is incomplete
▪ Expensive method
2.1.5. Hydrothermal synthesis of WO3 nano rods and their performance in the adsorption of
Rhodamine
in this method WO3 nano rods are used as a catalyst while the oxidant is Hydrogen peroxide.
It is an also environment friendly process. The yield for the process is 79% operated at 90 deg
C and 1 atm. pressure. The residence time for the process is 24 Hrs.
The disadvantages for not using this process are
▪ Lower yield
▪ Higher residence time
2.1.6. Dawson-type polyoxometalates as Green catalyst for Adipic Acid synthesis
In this method cyclohexene is used using Hydrogen peroxide as a oxidant while
Polyoxometalates are used as catalysts.
In chemistry, a polyoxometalate (abbreviated POM) is a polyatomic ion, usually an anion,
that consists of three or more transition metal oxyanions linked together by shared oxygen

9
atoms to form closed 3-dimensional frameworks. The process is operated at 1 atm pressure
and 90 deg C temperature. The yield for the process is 69%.
The disadvantages for this process are
▪ Lower yield
▪ Lower residence time
▪ Additional potential energy is required for slow kinetics of Polyoxometalate
▪ Lack of selectivity
2.2. Process Description:
The process selected is synthesis of Adipic Acid by direct combination of cyclohexene
with Hydrogen peroxide H2O2 using Sodium Tungstate. Sodium tungstate dihydrate is a
hydrated sodium salt of tungstic acid. It participates as a catalyst in the preparation of various
epoxides. Various crystallographic properties of sodium tungstate dehydrate have been
analyzed. It combines with Hydrogen peroxide for the oxidation of secondary amines to
nitrones. Hydrogen peroxide is a colorless liquid that is widely used as an oxidizer and
bleaching agent. Hydrogen peroxide decomposes over time to water and oxygen. Heat,
ultraviolet light, and contaminants accelerate its decomposition, so it should be stored in cool,
dark places. . Noroyi reported a practical method of oxidation cyclohexene with 30%
hydrogen peroxide in presence of small amounts of Na2WO4 and [CH3 (n-C8H17)3N]
HSO4 as a phase transfer catalyst. A novel clean per oxy tungstate-organic complex catalyst
was also used to catalyze oxidation of cyclohexene by 30% hydrogen peroxide to produce
adipic acid at a high yield (Ma et al., 2001). Long chain carbon alkyl ammonium sulfate was
used to substitute the expensive phrase transfer catalyst to produce adipic acid and obtained a
yield of 81.7% (Gong et al., 2000).

The process selection is based on the yield and environmental condition basis. It is an
environment friendly process with highest yield of 95%. The process is operated at 1 atm
pressure and 90 degree C temperature. Hydrogen peroxide is used as oxidant while sodium
tungstate as a catalyst. The catalyst is used to boast the reaction kinetics. The residence time
for the process is 20 Hrs. The residence time is provided to gave the contact time of the
reactants and to get maximum yield.

10
The process is operated at 90 deg C temperature. The cyclohexene is firstly oxidize to form
epoxide which is not a stable epoxide and reacted with H2O to form ketone cyclohexandiol.
This ketone on further oxidation is converted into adipic anhydride which on form adipic acid
by combination of water generated during the reaction.

2.3. Process Flow diagram:

Figure 4: Process Flow Diagram

11
Chapter 3

3. Material and Energy Balance

3.1. MATERIAL BALANCE
Plant capacity = 4500000 kg/ year
Production per hour = (4500000)/ (365*24) = 513.69 kg/hr
Basis: Unit hour operation
Further we will use the notations as under
cyclohexene Adipic Acid
3.1.1. Capacity of Plant:
We have selected the capacity of plant 4500000 kg/yr. because throughout the Pakistan
there is no plant for the production of Adipic Acid. Now new project is going on for the
installment of plant having 4500000-kg/yr. capacities.
Amount of Adipic Acid produced per day = 12383.76 kg/day
= 513.69 kg/hr.
The key to successful production of Adipic Acid is the reaction. So we assume that the
cyclohexene, which is used as a main component for production of Adipic Acid, is about
100% pure. The reaction conditions are:
Temperature= 90Co
Pressure= 1 atm
Residence time or Cycle time=20 hr.
Overall conversion at these conditions =95%
Serial # Component Inlet mass flow rate Outlet mass flow rate
Kg/day Kg/day
1 Cyclohexene 7288.82 364.44
2 Hydrogen peroxide 12088.77 604.44
3 Adipic Acid 14933.19 21013.13
4 Total 34310.77 34310.77
Table 3:Material Balance around reactor

Serial# Component Inlet mass flow rate Outlet mass flow rate Outlet mass of
Kg/day Kg/day recycle kg/day
1 C6H10 364.441 0 364.441
2 H2O2 604.438 604.438 0
3 C6H10O4 12328.767 12328.767 0
4 H2O 21013.126 21013.126 0
5 total 34310.77 33946.329 364.441
Table 4:Material Balance around Decanter

12
 Total inlet flow rate = 34310.77 Kg/hr
Total outlet flow rate = Outlet flow rate + Outlet recycle flow rate
= 33946.329 + 364.441
= 34310.77 Kg/hr
8.471 wt% Adipic Acid soluble in water at 50℃

Inlet(kg/day) Inlet(kg/day)

Crystals liquid
H2O2 604.438 0 604.438
C6H10O4 12328.767 10548.745 1780.022
H 2O 21013.126 0 21013.126
Total 33946.331 10548.745 23397.586
Table 5: Material Balance around crystallizer 1

Total inlet= 33946.331 kg/day

Total outlet= crystals + liquids=10548.745+23397.586
=33946.331 kg/day
2% moisture in crystals stream
Serial# Component Inlet mass flow rate Outlet mass flow rate Kg/day
Kg/day
Crystals Mother liquor
1 H2O2 604.4 0 604.4
2 C6H10O4 12328.8 11268.5 1060.3
3 H2O 21013.1 28.4 20984.8
4 Total 33946.3 11296.9 22649.5
Table 6: Material Balance around filter 1

Component Inlet flowrate kmol/day Outlet flowrate kmol/day

vapors liquids
H2O2 17.778 0 17.778
C6H10O4 7.262 0 7.262
H 2O 1165.82 1049.23 116.59
Total 1190.86 1049.23 141.63
Table 7:Material balance around evaporator

13
1.87 wt% Adipic Acid soluble in water at 20℃
Serial# Component Inlet mass flow rate Outlet Liquid mass flow rate Kg/day
Kg/day
crystals liquid
1 H2O2 604.438 0 604.438
2 C6H10O4 1060.274 1021.032 39.242
3 H2O 2098.477 0 2098.477
4 Total 3763.185 1021.032 2742.157

Table 8: Material balance around crystallizer 2

2% moisture in crystals stream
Serial# Component Inlet mass flow rate Outlet mass flow rate Kg/day
Kg/day
Crystals Mother liquor
1 H2O2 604.4 0 604.4
2 C6H10O4 1060.3 1021.5 39.2
3 H2O 2098.5 2.6 2095.5
4 Total 3763.2 1024.1 2739.1
Table 9: Material balance around filter 2

components Inlet kg/day Outlet kg/day

crystals vapors
C6H10O4 12289.526 12289.526 0
H 2O 30.921 3.092 27.829
Table 10: material balance around dryer

14
3.2. Energy Balance
According to law of conservation of energy
[Rate of Accumulation of Energy within system =Rate of Energy entering the system – Rate
of energy leaving the system + Rate of Energy generation]
1.1 For steady state system no accumulation of mass or energy with in system, so by
modifying above equation, and applying across each equipment, the energy balance of
each equipment is as under.
For case of energy balance across each equipment to determine the enthalpy of streams we
used reference temperature equal to 25 degC.
Q= m Cp ∆T
T = Tr − Ti

3.2.1. Around heat exchanger#1:

QC = -QH
QC = mCP∆T QH = m⅄

CYCLOHEXENE STEAM
M 7288.82 kg/day Qh 9.6 x 10^5kJ/day
T1 293 k
⅄ 2209.70 kJ/kg
T2 363 k
m 434.89 kg/day
Qc 1.6 x 10^5 kJ/day

3.2.2. Around heat exchanger 2:

QC = -QH
QC = mCP∆T QH = m⅄
30% Hydrogen peroxide steam
M 12088.77 kg/day
T1 293 k Qh 3715376.72 kJ/day
T2 363 k
⅄ 2209.70 kJ/kg
Qc 3715376.72 kJ/day
m 1681.39 kg/day

3.2.3. Around Chemical Reactor

∑ӨiCpi(T-Tio)+∆HrxX =0
Conversion = X = 0.95
Capacity = 12328.767 kg/day of Adipic Acid

15
Heat Units Values
∑ӨiCpi(T-Tio) kJ/mol 38157.2
∆Hrx.X kJ/mol -1236946.6
T1 K 363
T2 k 393.8

3.2.4. Around heat exchanger 3:

QC = -QH
Qh = mCP∆T Qc = mCp(T2-T1)

Product WATER

T1 393.8 K Qc 3653422.97 kJ/day

T2 363 K T1 293 K

Qh 3653422.97 kJ/day T2 298 K

m 536.833 kg/day

3.2.5. Around crystallizer#1:

Qh = ∆Hcrys+∆H
Product stream
∆H (kJ/day) 90-50℃ -4668842.136kJ/day
∆Hcrys (kJ/day) 50℃ -2798582.111kJ/day
QH (kJ/day) -7467424.248kJ/day

QC = QH
QC = mCp∆T
water
mH2O kg/day 20-25℃ 355511.6877 kJ/day

3.2.6. Around heat exchanger #4:

QC = -QH
QC = mCP∆T QH = m⅄

steam
PRODUCT
Qh 1371726.80 kJ/day
T1 323 K
⅄ 2209.70 kJ/kg
T2 358K
m 620.78 g/day
QC 1371726.80kJ/day

16
3.2.7. Around Evaporator:
mCp(T2-T1) + mv⅄v = ms⅄s
mCp(85-110)+ (m⅄)v = (m⅄)steam
liquid (85-110 oC)
Cp(85-110) m mCp(85-110)
(kJ/kmol) (kmol/day) (kJ/day)
H2O2 2278.556 17.778 40507.262
C6H10O4 8392.391 7.262 60946.806
H2O 1887.396 1165.821 2200365.412
2301819.481

vapour (110 oC)

m ⅄ m.⅄
(kmol/day) (kg/day) (kJ/kg) (kJ/day)
H2O2
C6H10O4
H2O 1049.239 18886.296 2232.960 42172343.697

steam (125 oC)

⅄ m
s
(kJ/kg) (kmol/day)
H2O2
C6H10O4
H2O 2209.700 1050.236

3.2.8. Around heat exchanger# 5:

QC = -QH
Qh = mCP∆T Qc = mCp(T2-T1)

Product WATER

T1 393.8 K Qc 321490.61 kJ/day

T2 363 K T1 293 K

Qh 321490.61kJ/day T2 298 K
m 850.31 kmol/day

17
 3.2.9. Around crystallizer#2:
Qh = ∆Hcrys+∆H
rys1∆Hcrys
∆Hcrys-∆H1=q (h)
H1 ∆Hcrys q (h)
(kJ/day)
m(kmol/day m
) ∆Ho (kg/da ∆Hcrys
Cp(kJ/kmol) H1 (kJ/day)
(90-50 oC) m.Cp (kJ/kg) y) (kJ/day) -779045.614
-
1021.0 270879.9
H2O2 17.778 3569.157 63451.048 -265.300 32 08
C6H10O4 7.262 12985.003 94299.044
H2O 116.582 3005.742 350415.614
-508165.706

QC = QH
QC = mCp∆T(25-20 oC)
m = q/Cp.∆t

Cp.∆t (293-298) q (h) m m

(kJ/kmol) (kJ/day) (kmol/day) (kg/day)
H2O 378.085 779045.614 2060.503892 37089.07006

3.2.10. Around heat exchanger # 6

QC = -QH
QC = mCP∆T QH = m⅄

PRODUCT steam
T1 Qh 65036.28kJ/day
293.00
T2
323.00 ⅄ 2209.70 kJ/kg
QC 65036.28kJ/day m 29.43 kg/day

3.2.11. Around Dryer:

Qheater = ( (Tin-Ta)(ms(Xin-Xout)∆Hv + msCps(Tout-Tin) + Qloss)/ (Tin-Tout)
Qheater = ma.Cpa.(Tain-Taout)

18
Tin(K)
423
323Tout(K) 383Ta(K)
(Tin-
Ta)/(Tin-
Tout)
Cps(50-
110 oC) m ms.Cps Hv mv Hv.mv Qheater
(kJ/kmol) (kmol/day) (kJ/day) (kJ/kmol) (kmol/day) (kJ/day) (kJ/day)
C6H10O4 19717.939 84.175 1659754.220 40706.000 1.546
H2O 4516.759 1.718 7759.131
-1667513.351 62934.259 1.667 -
2674298.4
87

Qheater = ma.Cpa.(Tain-Taout)
Tain (K) 423 Taout (K) 383

Cpa (150-110 oC) Tout-Tin m

(kJ/kmol) K (kmol/day)
Air
4539.186266 40 589.1581289

19
Chapter 4

4. Detailed Equipment Design

This chapter will cover the design of each equipment used in the whole process in detail
according to the required production rate and capacity. Following equipments are designed
below:
• Reactor
• Decanter
• Crystallizer
• Filter
• Evaporator
• Dryer Heat Exchanger
4.1. Reactor:
Reactor is considered to be the most important part of reactor of any process plant.
There are different types of reactor. Depending upon the requirement of process, selection of
reactor is carried out.
4.1.1. Types of reactor:
Following are the few types of reactor:
1. Batch reactor
2. Continuously Stirred Tank Reactor (CSTR)
3. Plug Flow Reactor (PFR)
4.1.1.1. Batch Reactor:
The principle of working of a batch reactor is the addition of all reactants in the
reactor at the same time and then allow the reactants to react for the required time (residence
time) and then all material including the reactant and product are extracted and washed out
the reactor. Following are the limitations of batch reactor:
• Suitable for small scale production.
• Suitable when different types of products are to be produced at the same time.
• Suitable for reaction of higher selectivity.
• Suitable for reactions requiring long reaction time.
4.1.1.2. Plug Flow Reactor:
The plug flow reactor is characterized by the flow of two or more reagents through a pipe
or tubes. There is a continues gradient of concentration in the direction of flow.
Limitations of plug flow reactor are:
• PFR are not suitable where intense mixing is required

20
 • Reagents can be introduced at any point other than entrance point
• Tubular reactors are usually preferred when considerable heat transfer is
required.
• Suitable for high temperature and pressure conditions
4.1.1.3. Continuously Stirred Tank Reactor (CSTR):
CSTR is characterized with a tank and impeller in which one or more reagents are
introduced in it, while the reactor effluent is recovered. CSTR has following
characteristics:
• High flexible device
• By-products may be removed in between the reaction
• Reaction can be carried out in horizontal as well as vertical direction
• High degree of agitation can be achieved
4.1.1.4. Selected Type of Reactor:
Continues Stirred Tank Reactor is the type of reactor that we are using for the
production of adipic acid as it requires intense mixing because of the presence of two
different phases. CSTR is preferred to have a better control over the product formation,
convenient operation of the system and easy automation of the entire process. It provides
simple pH and temperature control, simple catalyst charging and displacement. Continuous
process is preferred in order to improve the productivity and efficiency.

Figure 5: continuously stirred tank reactor

21
4.1.2. Continuously Stirred Tank Reactor and its Operation:
Since the process is all about the production of adipic acid through green pathway using
hydrogen peroxide as an oxidizing agent. The only by-product is water and the conversion
resulting from the optimum condition is 95%. Following is the reaction occurs during the
process:
C6H10 + 4H2O2 C6H10O4 + 4H2O

Na2WO4 and [CH3(n-C8H17)3N]HSO4 are used as surfactant that helps in the emulsion of
two phase liquids. Heterogeneous catalyst can be employed as,
• Fixed bed
• Fluidized bed
We have selected fixed bed tubular reactor because of following reasons,
• High conversion rate per unit weight of catalyst.
• Separation from product is not required.
• Effective at high temperatures and pressures.

4.1.3. Known Parameters and Assumptions:

Known parameters of the reactor are:
• Isothermal process
• 1st order reaction
• Temperature = 368 K (95oC)
• Pressure = 1 atm
• Rotational speed of stirrer = 1400 rpm
• Conversion = 95%
Following are the assumption taken during the design of reactor:
• Well mixed
• All reactants enter at same time
• No side reactions
• Negligible filling time
• Water is in excess Cb0 = Cb
• L/D = 1.3

22
4.1.4. Design calculations:
To determine the volume of reactor, we have to calculate the rate of reaction. This is
calculated from the experimental data of time versus conversion, the slope of the graph will
give us the value of rate constant. Following calculations results in the value of rate constant:
-k t = ln[(Cao-Cc)/Cao]

Figure 6: graph for time vs conversion

Formula used for calculating the volume of reactor is:

V= Fao*X/ -ra

23
4.1.5. Specification sheet of reactor:

Table 11:Specification Sheet of Reactor

24
4.2. Crystallizer
Crystallization means the formation of solid particles in a homogeneous phase. In the form of
ice, it can be caused by the formation of solid particles in the vapor; In the formation of large
single crystals, as solidified from the melting of liquids; Or crystallization from liquid
solution.
4.2.1. Types of Continuous Crystallizers
4.2.1.1. Forced-Circulation Crystallizer
• Least expensive type of crystallizer.
• Large range of sizes available.
• Used for fine crystals.
• Suitable for High Density slurries.
4.2.1.2. Draught-Tube Agitated Vacuum Crystallizer
• Suitable for large capacity.
• Suitable for low density slurries.
• A bit expensive than other types of crystallizers.
• Not energy efficient.
4.2.1.3. Fluidized-Bed Crystallizer
• Suitable for large capacity.
• Suitable for low density slurries.
• A bit expensive than other types of crystallizers.
• Not energy efficient.
4.2.2. Selection:
Selected type of crystallizer is “Forced-Circulation Crystallizer”, because
▪ Produces fine crystals.
▪ Suitable for low capacity.
▪ Suitable for high density.
▪ Least Expensive.
4.2.3. Design Steps
▪ Growth Rate Calculation
▪ Population Balance
▪ Magma Density
▪ Nucleation Rate Calculations
▪ Volume of Vessel Calculations
▪ Power of Pump Calculations

25
4.2.4. Thermo-Physical Properties and Assumptions:
Sr. No. Specifications Inlet Outlet

1. Mass Flowrate (Kg/hr) 1414.43 1414.43

2. Temp (℃) 90 50

5. Viscosity (Pa.s) 0.0013 0.00098

6. Density (Kg/m3) 982.49 992.700

Table 12:thermophysical properties

Assumptions
▪ Assuming spherical crystals, the volume shape factor will be:
α = (36ℼ)1/3
α = 4.84
▪ Median Size of Crystal LM (m) = 0.00025
Growth Rate Calculations
G= (30/α.Ꝭc.KR.LM4)1/i-1

Crystal Density ꝭc = 1360 Kg/m3

Growth Rate Constant KR = 4*10^18 s/m2.Kg

Median Size of Crystal LM = 0.00025 m

Volume Shape Factor α = 4.84
Rate Order i = 2
G = 0.00105 m/hr
Residence Time
Ꞇ = LM/3.67G
Ꞇ = 0.0648 hr
Population Balance
n = noexp(-LM/GꞆ)
Population Density of Nuclei
no = KRGi-1
no = 1.17*10^12

26
Crystal Population Density
n = 2.97*10^10
Number of Crystals
NT = n0GꞆ
Nt = 7.95 x 10^7
Magma Density
MT = 6αꝭcn0(GꞆ)4
MT = 0.99 Kg/m3
Magma Discharge Flowrate
Q = Pc/MT
Flowrate of crystals Pc = 439.53 Kg/hr
Q = 442.98 m3/hr
Nucleation Rate
B = KRMTjGi = 1.22 x 10^9 m/hr
Volume of Vessel
V = QꞆ = 28.71 m3
Dominant Size of Crystal
LD = 3GꞆ = 2.04 x 10^-4 m
Power of Pump
Capacity = 6.34 gpm
Assume
RPM = 3540
Power = ṁ.∆H/ἡ = 0.48 hp

27
4.2.5. Design Specifications Sheet

DESIGN SPECIFICATIONS SHEET

IDENTIFICATION
Name of Equipment Crystallizer
Type MSMPR Forced-Circulation Crystallizer
Function To crystallize Adipic Acid from Adipic Acid
Solution via cooling
Number of Units 1
Capacity 442.9 m3/h
Operation Continuous
Basic Design Data
Pressure 1 atm
Temperature Range 50 - 90
Density 992.7 Kg/m3
Residence Time 0.065 h
Vessel Design
Design Pressure 9.96 atm
Vessel Volume 28.71 m3
Pump Design
Type Positive Displacement
Capacity 6.34 gal/m
Power 0.48 hp
Table 13:Specification sheet of Crystallizer

4.3. Separator:
4.3.1. Objective:
To find the area of separating tank required for the purpose of separation.
4.3.2. Description:
Separators work on the principle that the two or three components have different densities,
which allows them to stratify on the basis of their densities. Any solids such as sand will also
settle in the bottom of the separator.
4.3.3. Significance in Process
The basic aim of air project to separate water and adipic acid and improve the concentration
of adipic acid.
Types of Separator Advantages Disadvantages
Horizontal two phase • Large liquid solid • The separator is not
separator interphase sound for sand
• For two phase containing conditions
mixture • Inconvenient high
• Perfect separation level errection
effect
• Flexible design
• Easy to install

28
 • Low transportation
and installation cost

Horizontal two phase • Large gas liquid • Not easy for cleaning
barrel separator interphase • High requirement for
• For two phase level control
mixture
• Perfect separation
effect
• skid-mountable
design
• for small diameter

Horizontal three phase • Large gas liquid solid • Large occupied area
separator interphase • Not easy for cleaning
• For two phase • Inconvenient high
mixture level errection
• Perfect separation
effect
• Flexible design
• Easy to install

Vertical two phase • Easy to clean • Large separator

separator • For two phase diameter
mixture • High cost
• Sensitive level • Inconvenient for
controlling transportation
• less occupied area
Vertical three phase • Easy to clean • Large separator
separator • For three phase diameter
mixture • High cost
• Sensitive level
controlling
• less occupied area
• Large space for gas
liquid separation
Table 14: comparison of different separators
4.3.4. 2-phase horizontal Separator
It has been selected due to following reasons:
• Good Mechanical Layout
• Perfect separation effect
• Easily Cleaning
• Low transportation and low installation cost
• Well established Design Procedures.

29
4.3.5. Design of Separator:
Design step
1. Calculate Flow rates, Temperatures of streams.
2. Collect together the fluid physical properties required.
3. Selection of the type of separator to be used
4. Calculate settling velocity
5. Calculate the area required.
Step 1:
• Viscosity of water = 0.0007

• Pressure = 1 atm
• Diameter of globules= 0.000051 m
• Density of water = 992

• Density of Adipic Acid= 1340

• g= 9.8

Step 2:

Calculating Settling velocity vm= = 58.4

Calculating F = = 1.753

Calculating L= = 0.00254

Calculating = mass rate of solid feed = 4477.63

Step 3:

Calculating the Area of separating tank =

Area of separating tank = 0.15 m2

30
4.3.6. Design Specification Sheet:
DESIGN SPECIFICATIONS SHEET
IDENTIFICATION
Name of Equipment Separator
Type 2-phase horizontal separator
Function To separate adipic acid crystals
Number of Units 2
Separation Capacity 33941 Kg/day
Operation Continuous
Basic Design Data
Pressure 1 atm
Temperature Range 85 - 110
Density 1340.65 Kg/m3
Separating system Design
Fluid Handled Adipic Acid L 0.00252
Solution
Viscosity 0.0007 4477.63
Temperature 85℃
Diameter of 0.000051 m Area of 0.15 m2
globules separating tank
% filled 90%
Settling velocity 58.4

Table 15: Specification sheet of separator

4.4. Evaporator
In the evaporation process, concentration of a product is accomplished by boiling out a
solvent, generally water. It is a unit operation that is used extensively in processing foods,
chemicals, pharmaceuticals.
While the design criteria for evaporators are the same regardless of the industry involved, two
questions always exist: is this equipment best suited for the duty, and is the equipment
arranged for the most efficient and economical use? As a result, many types of evaporators
and many variations in processing techniques have been developed to take into account
different product characteristics and operating parameters.
4.4.1. Types of Evaporator
4.4.1.1. Falling-Film Evaporator:
• Either plate or tubular, provides the highest heat transfer coefficients.
• It is usually be the most economic.
• It is not suitable for the evaporation of products with viscosities over 300cp.
• It is not suitable for products that foul heavily on heat transfer surfaces during boiling.

4.4.1.2. Forced Circulation Evaporators:

31
 • It can be operated up to viscosities of over 5,000cp.
• It will significantly reduce fouling.
• It is expensive; both capital and operating costs are high.
4.4.1.3. Paravel Evaporators:
• These are suitable for viscosities up to 10,000cp for low fouling duties.
• These are suitable for very high viscosities, i.e., over 20,000cp, usually the only
suitable evaporation modes are the wiped film and thin film systems.
4.4.2. Selection Criteria
➢ High Heat Transfer Coefficient
➢ Heat Economy
➢ Cost
➢ Viscosity

Figure 7:Long tube falling film evaporator

4.4.3. Long Tube Falling-Film Evaporator

Selected type of Evaporator is, “Long tube Vertical Falling-Film Evaporator”.
Because:
✓ Tubular Falling–Film Evaporator provides the highest heat transfer coefficient.
✓ It is the most economic evaporator.

32
 ✓ It is suitable for the viscosities less than 300cp.
✓ It requires less floor space.
4.4.4. Number of Effects
• With the increasing number of effects, the capital cost also increases.
• Heat economy for efficient single-effect evaporator is around 1. It increases for
double or multiple-effect evaporators.
• Multiple-effect evaporators are not suitable for evaporation rate lower than 1350
Kg/hr
Here Single-Effect Evaporator is used because:
✓ Heat Economy is 0.99.
✓ The Evaporation rate required is 786.93 Kg/hr.
✓ It is will be most Economic.
4.4.5. Design Steps
• Assumptions and Fluid Allocation
• Heat Transfer Area Calculation
• Calandria Design
• Overall Heat Transfer Coefficient Calculation
• Corrected Heat Transfer Area
Thermo-Physical Properties

Sr. No. Specifications Steam Process Stream

1. Mass Flowrate (Kg/hr) 787.68 943.73

2. Temp(In/Out) (℃) 125/125 85/110

3. Specific Heat (KJ/Kg.K) 2.015 4.41

4. Thermal Conductivity (W/m.K) 0.038 0.688

5. Viscosity (Pa.s) 0.000014 0.00032

3
6. Density (Kg/m ) 1.29 956.65

Table 16: thermo-physical properties

33
4.4.6. Assumptions and Fluid Allocation
▪ Process Stream will entre from above in the tubes.
▪ Steam will entre in shell.
Assume overall heat transfer coefficient
Ud = 2350 (W/m2.K)
Heat Economy = Kg of steam/Kg of vapours
Heat Economy = 0.99
Heat Transfer Area Calculation
A = Q/Ud.∆T
Q = 483480.52 W
Ud = 2350 (W/m2.K)
∆T = 15 K
A = 13.72 m2
Calandria Design
Tube Side Calculations
Assuming the tube-side specifications on the basis of TEMA standards
Tube OD = 0.0254 m
Tube ID = 0.0212 m
B.W.G No. = 14
Tube Length = 6 m
Area of tube = ℼ.Do.L
Area of tube = 0.479 m2
Number of tubes = Heat transfer area/Area of tube
Nt = 29
Corrected Heat Transfer area = Nt(Area of Tube)
Corrected Heat Transfer area = 13.88 m2
Calandria Shell Calculations
Db = Do(Nt/k)1/n
For Triangular Pitch
k=0.249, n=2.207 From the fig 8
Db = 0.22 m
Shell Dia DS = Db+C
Shell Clearance C = 0.017 m From Fig 9
DS = 0.24 m

34
Figure 8:Constants to be used in correlation

Figure 9:Shell Clearance

4.4.7. Design Overall Heat Transfer Coefficient

Required Overall Heat Transfer Coefficient
Ur = Q/(Nt.ℼ.Do.L.∆T)
Ur = 2321.42 (W/m2.K)
Tube Overall Heat Transfer Coefficient (hi)
In Evaporator calculation of Ud requires that whether boiling or evaporation is nucleate or
film. to calculate this we need to first calculate boiling heat-transfer coefficient by using The
Forster-Zuber correlation. R.W. Serth, in Process Heat Transfer, 2007
hb = [(0.001229)(kl0.79)(Cp0.45)(Ꝭl0.49)(∆T0.24)(∆Psat0.75)]/[(σ0.5)(μl0.29)(⅄0.24)(Ꝭv0.24)]
kl = 0.687 W/m.K
Cpl = 4.411 KJ/Kg.K

35
Ꝭl = 956.65 KJ/Kg.K
∆T=Tw – Tsat
Tsat (1 atm) = 372.97 K
TW = 398 K
Psat (Tw) = 232581.405 Pa
Psat (Tsat) = 101223.68Pa
σ = 0.0565 N/m
μl = 0.000318 Pa.s
⅄ = 2229.6 KJ/Kg
Ꝭv = 0.8206 Kg/m3
∆T = 25.03 K
∆Psat = 131357.725 Pa
hb = hi = 5510.53 W/m2.K
Shell-side Heat Transfer Coefficient
As we are using steam for heating purpose, the condensing coefficient of steam will be:
ho = 8500 W/m2.K
Now the Dirt Factor will be
Rd = 0.000117 m2.K/W
Clean Overall Coefficient
Uc = (hi*ho)/(hi+ho)
Uc = 3343.16 W/m2.K
Design Overall Heat Transfer Coefficient
Ud = (1/Uc+Rd)-1 = 2399.43 W/m2.K
Over-Design Check
Over-Design = [(Ud/Ur)-1]*100
Over-Design = 3.36%
Evaporator is 3.36% over-designed which can be neglected as Safety Margin.
Corrected Heat Transfer Area
A = Q/Ud.∆T
Q = 483480.52 W
Ud = 2399.43 (W/m2.K)
∆T = 15 K
A = 13.43 m2
Nt = 28

36
4.4.8. Design Specifications Sheet

DESIGN SPECIFICATIONS SHEET

IDENTIFICATION
Name of Equipment Evaporator
Type Long-Tube Falling-Film
Function To concentrate solution Adipic Acid
Number of Units 1
Evaporation Capacity 786.9 Kg/h
Operation Continuous
Basic Design Data
Pressure 1 atm
Temperature Range 85 - 110
Density 956.65 Kg/m3
Heat Transfer Area 13.43 m2
Heating System Design
Tube Design Shell Design
Fluid Handled Adipic Acid Fluid Handled Saturated Steam
Solution
Mass Flowrate 943.73 Kg/h Mass Flowrate 787.68 Kg/h
Temperature 85℃ Temperature 125℃
Outside Diameter 0.0254 m Shell Diameter 0.236 m
Inside Diameter 0.0212 m Clearance 0.017 m
B.W.G No. 14
Tube Length 6m
Number of tubes 28
Bundle Diameter 0.219 m
Table17 :specification sheet of Evaporator

4.5. Dryer:
4.5.1. Objective:
To find the volume and residence time required for the purpose of drying.
4.5.2. Description:
The industrial dryer is employed to reduce or minimize the liquid moisture content of the
material it is handling by bringing it into direct contact with a heated gas.
4.5.3. Significance in Process
The basic aim of our project to dryer the crystals of adipic acid.
Types of Dryer Advantages Disadvantages
Fluidized bed dryer • Efficient heat and mass • Generation of charges
transfer • May cause attrition
• Individual and uniform • Loss of fine particles
drying • Not environment
• Short drying time friendly
• Used in pharmaceutical
companies

37
Rotary dryer • For large production • heat lost in large
capacity • One time installation
• Low maintenance cost cost is high
• Flexibility in operation • Installation and
• Simple structure removal difficult
• Continuous operation
Rolling bed dryer • Suitable for heat • High maintenance cost
sensitive material • Not suitable for less
• Compact size soluble salt solutions
• Complete drying
Conduction Dryer • Simple in handling • Not suitable for lumped
• Lesser capital cost material
• Short contact time • Non uniform residence
• Requires small area time

Convection Dryer • Fast volumetric drying • product texture may be

• Higher drying rate effected
• Reduced energy • Large space required
consumption • High labor contact
• Lower operating cost
Table 18: Comparison of Different types of separators

4.5.4. Rotary dryer

It has been selected due to following reasons:
• Rotary dryers are less sensitive to particle size.
• Low maintenance cost; thus economical.
• It has the greatest capacity than any type of dryer.
4.5.5. Design of Separator:
Design step
1. Calculate Flow rates, Temperatures of streams.
2. Collect together the fluid physical properties required.
3. Selection of the type of dryer to be used
4. Calculate cross-sectional area of dryer
5. Calculate the diameter of dryer
6. Calculate LMTD.
7. Calculate dryer Length
8. Calculate Dryer Volume
9. Calculate residence time
Step 1:
Conditions:
• Pressure = 1 atm

38
 • Relative Humidity= 0.60
• X1= 0.90
• X2= 0.10
• Nt= 1.5 (Assumption)
Step 2:
• Mass of air = 170856.11

• Allowable gas velocity= 2408680

• Thb= 383 K
• Tha = 327.9 K
• Qt= 10600000000

Step 3:

Calculating Cross-sectional Area = = 7.093 m2

0.5
Calculating Diameter of dryer = = 3.1 m

Calculating Length of dryer = = 3.53 m

Calculating Volume of dryer = (L D) 2 = 36.75 m3

Calculating residence time or drying time = = 36 min

39
4.5.6. Design Specification Sheet:

DESIGN SPECIFICATIONS SHEET

IDENTIFICATION
Name of Equipment Dryer
Type Rotary dryer
Function To dry adipic acid crystals
Number of Units 1
Separation Capacity 85.8 Kmol/day
Operation Adiabatic drying
Basic Design Data
Pressure 1 atm
Temperature Range 368
Dryer system Design
Crystals Adipic Acid Cross-sectional 7.093 m2
Handled crystals area of dryer
Allowable gas 2408680 Diameter of 3.1 m
velocity dryer
Temperature 368 Length of 3.53 m
% Relative 60% dryer
humidity Volume of 36.75 m3
Moisture 0.90 dryer
content
Residence time 36 min

Table 19: Specification Sheet of Dryer

4.6. Heat Exchanger

A heat exchanger is a system used to transfer heat between two or more fluids. Heat
exchangers are used in both cooling and heating processes. The fluids may be separated by a
solid wall to prevent mixing or they may be in direct contact
4.6.1. Types:
➢ Parallel-flow and counter-flow heat exchanger.
➢ Finned and Unfinned tubular heat exchanger.
➢ U-tube, single pass straight and two pass straight heat exchanger.
➢ Plate-and-frame heat exchanger.
➢ Pate-fin heat exchanger.
➢ Microchannel heat exchanger.
➢ Shell and tube
➢ Double pipe
4.6.1.1. Parallel flow heat exchanger:
In in line exchangers, the hot and cold fluids move parallel to each other. In Parallel flow heat
exchangers, the outlet temperature of the "cold" fluid can never exceed the outlet temperature

40
of the "hot" fluid. The exchanger is performing at its best when the outlet temperatures are
equal.

4.6.1.2. Cross flow heat exchanger:

A cross-flow heat exchanger is used in a cooling and ventilation system that requires heat to
be transferred from one airstream to another. A cross-flow heat exchanger is made of thin
metal panels, normally aluminium. The thermal energy is exchanged via the panels.

4.6.1.3. Counter flow heat exchanger:

A counter-flow heat exchanger is one in which the direction of the flow of one of the working
fluids is opposite to the direction to the flow of the other fluid. In a parallel flow exchanger,
both fluids in the heat exchanger flow in the same direction.

4.6.1.4. Finned tubular heat exchanger:

Finned tube exchangers are known for maximizing heat transfer surface area, by
design. Finned tube heat exchangers have tubes with extended outer surface area or fins to
enhance the heat transfer rate from the additional area of fins

41
4.6.1.5. Un-finned tubular heat exchanger:
With a finned tubular heat exchanger, both fluids are unmixed, the one between the fins is
guided in a direction transverse to the tube flow direction. In the un-finned exchanger heat
can be exchanged in all directions, and the fluid can mix.
4.6.1.6. Micro channel heat exchanger:
The micro heat exchanger is a device in which the fluid flows in lateral channel with typical
dimensions below 1 mm. The diagram below refers to a microchannel heat exchanger.
4.6.1.7. Shell and tube type heat exchanger:
The shell-and-tube heat exchanger can be adapted in a compact heat exchanger, using
polymer tubes. With the reduction of the polymer tube diameter, the shell can accommodate
more tubes, hence, increasing heat transfer area density. Polymer materials are light and resist
to corrosion but they are limited to ?? temperatures and pressures.
4.6.1.8. u-tube single and 2 pass heat exchanger:
The U-tube heat exchanger is a version of the tube bundle heat exchanger. The advantages lie
within its compact design and is therefore very efficient. Heat stress can be compensated for
due to the U-shaped in 2 pass u tube heat exchanger 2 passes of heat exchanging is used

4.6.1.9. Double pipe heat exchanger:

In these exchangers one fluid flows inside the tube and the other fluid flows on the outside.
Although they are simple and cheap, their low efficiency coupled with the high space
occupied in large scales, has led modern industries to use more efficient heat exchangers.
4.6.1.10. Plate type heat exchanger:
A plate heat exchanger is a type of heat exchanger that uses metal plates to
transfer heat between two fluids. This has a major advantage over a conventional heat
exchanger in that the fluids are exposed to a much larger surface area because the fluids are
spread out over the plates. This facilitates the transfer of heat, and greatly increases the speed
of the temperature change. Plate heat exchangers are now common and very
small brazed versions are used in the hot-water sections of millions of combination boilers.

42
The high heat transfer efficiency for such a small physical size has increased the domestic hot
water (DHW) flowrate of combination boilers. The small plate heat exchanger has made a
great impact in domestic heating and hot-water. Larger commercial versions
use gaskets between the plates, whereas smaller versions tend to be brazed.

4.6.1.11. Selected Heat Exchanger

Double pipe heat exchanger is selected for the heat transfer of cyclohexene and 30%
Hydrogen peroxide. The selection of heat exchanger is always based on Heat Transfer Area
of the stream. Double pipe heat exchanger is always used when the haet transfer area is
always less than 100 . The hot fluid is moved through the outer pipe while cold fluid move
through the inner pipe.

4.6.2. Known parameters and assumptions:

The known parameters for heat exchanger of hot and cold streams are:
➢ Temperature of inlet cold stream
➢ Temperature of outlet cold stream
➢ Temperature of inlet hot stream
➢ Temperature of outlet hot stream
➢ Flowrate of cold stream
➢ Specific heat of both cold and hot streams from D.Q kern
➢ Viscosity of both cold and hot stream from D.Q kern and Aspen plus
➢ Thermal conductivity of both cold and hot stream from Aspen plus

43
Unknow
➢ Flow rate of cold stream
➢ Heat duty
➢ Overall heat transfer coefficient
➢ Clean coefficient
➢ Pressure drop on both Annulus and inner pipe side
Assumption
➢ IPS of Annulus
➢ IPS of inner pipe
➢ Fouling factor
➢ Length of hair pins
➢

4.6.3. HYSYS Simulation:

Following images shows the results of parameters simulated on Aspen HYSYS:

Figure 10: HYSYS results of performance indicators on Heat Exchanger

Figure 11: HYSYS results of streams

44
4.6.4. Design Specification Sheet:

DESIGN SPECIFICATIONS SHEET

IDENTIFICATION
Name of Equipment Heat Exchanger
Type Double pipe
Function Heat exchange
Number of Units 6
Basic Design Data
Pressure 6 bar
Temperature Range 20 - 90
Heat Transfer Area 11.196 m2
Heating System Design
Annulus Inner pipe
Fluid Handled Steam Fluid Handled Cyclohexene
Mass Flowrate 1431.441 lb/hr
Temperature inlet 392 deg F Mass Flowrate 669.5 lb/hr
Temperature 332 deg F Temperature inlet 68 deg F
outlet Temperature 194 deg F
Outside Diameter 0.198 m outlet
Inside Diameter 0.2557 m Outer Diameter 0.198 m
Length of hairpin 6 ft Inner diameter 0.172 m
ho 213.09 hi 24.74

Table 20: Specification Sheet of Heat exchanger

4.7. Decanter:
A decanter centrifuge (also known as solid bowl centrifuge) separates continuously solid
materials from liquids in the slurry, and therefore plays an important role in the wastewater
treatment, chemical, oil, and food processing industries

45
4.7.1. Types
➢ Horizontal Decanter
➢ Vertical Decanter
➢ Hydrocyclones
➢ settling
➢ sedimentation
➢ Floation
➢ Centrifugal
4.7.1.1. Vertical Decanter:
The typical proportions of a vertical liquid gas separator are shown. The diameter of the
vessel must be large enough to slow the gas down to below the velocity at which the particle
will settle out. So minimum allowable diameter will be given as

D=

D= minimum vessel diameter

=gas or vapors flow rates m3/s
= if demister pad is used and 0.15

4.7.1.2. Horizontal decanter

A horizontal decanter would be selected on the basis of long liquid hold up time is required.
The diameter length and liquid level would be choosen to give sufficient liquid residence
time.
4.7.1.3. Hydrocyclone decanter
When the mixed liquid to be separated enters the hydrocyclone at a certain pressure from the
feed port of the hydrocyclone, a strong three-dimensional elliptical strong rotational shear
turbulence is generated. Due to the different density of particles, the centrifugal force,
centripetal buoyancy, fluid drag force and other sizes are different. Under centrifugal
sedimentation, most of the coarse particles (or heavy phases) are discharged through the
underflow port of the cyclone, while most of the fine particles (or light phases) are discharged
by the overflow pipe, thus achieving the purpose of separation and classification
4.7.1.4. Settling decanter
In settling processes, particles are separated from a fluid by gravitational forces acting on the
particles. The particles can be liquid drops or solid particles and the fluid can be a liquid or a
gas, in other words settling may be used for emulsions (L-L), aerosols (L-G), suspensions
(SL) and smoke(S-G).

46
4.7.1.5. Sedimentation decanter
Sedimentation is the separation of suspended solid particles from a liquid mixture by gravity
settling into a clear fluid and a slurry of higher solids content. Sedimentation can be done in a
thickener, in a clarifier or in a classifier. Since thickening and clarification are relatively
cheap processes when used for the treatment of large volumes of liquid, they are used for pre-
concentration of feeds to filtering.
4.7.1.6. Flotation decanter
Flotation is a gravity separation process which exploits differences in the surface properties
of particles. Gas bubbles are generated in a liquid. The bubbles become attached to solid
particles or immiscible liquid droplets causing the particles or droplets to rise to the surface
where they accumulate as a floating sludge. Flotation is used to separate mixtures of solid-
solid particles and liquid-liquid mixture of finely divided immiscible droplets.
4.7.1.7. Centrifugal decanter
Centrifugal separation is used when gravity separation (settling, sedimentation or flotation) is
too slow and the particles do not settle readily or at all . Gravity separation may be too slow
because of the closeness of the densities of the particle and the fluid, or because of
association forces holding the components together, as in emulsions. In centrifugal separation
processes, the separation of particles from a fluid is accomplished by centrifugal forces acting
on the particles. Centrifugal separators make use of the common principle that an object
whirled about an axis at a constant radial distance from the point is acted on by a force.
4.7.1.8. Selection of design equipment
Horizontal decanter is selected as design equipment on basis of separation of source of oil
and liquid sepration and residence or hold up time contact time or area of contact of oil and
liquid. The separation is truly based on density of oil and liquid.
4.7.2. Design equipment criteria
Flowrates density temp dynamic viscosity
Adipic acid 44.17 kg/hr 1360 kg/m3 50 deg c 0.0005465 Ns/m2
Water 874.36 kg/hr 1000 kg/m3 50 deg c 0.0414 Ns/m2
Ud=
Ud=settling velocity of dispersed phase droplet, m/s
Uc=velocity of continuous phase droplet, m/s
dd= droplet diameter, m
∂d= density of dispersed phase, kg/m3
∂c= density of continuous phase, kg/m3
g= gravity, m/s2
dd= 150 micro m (Assume)
Ud= 0.00806 m/s

47
Lc= o.000242 m3/s ( vol. flowrate of water)
Ai= =0.442 m2

Ai= area of interface

r= =0.37

Diameter=2xr=0.37
Height is twice of diameter
H=2xD= 1.5 m
Take dispersion band as 10% of the height= 0.15 m
Check residence time of droplet= =274 se= 5 mint

Time is satisfactor and is normally recommended

Check water size (continuous phase)

Velosity of oil phase= x =0.000462 m/s

dd= =139micro m

4.7.3. Piping arrangement

Flowrate =2.519x10^-4 m3/s
Flowrate= area of pipe x velocity of fluid
Velocity of fluid = 1 m/s for pipe safety

Area of pipe= =2.519x10^-4

Pipe diameter= =0.0179 m = 20 mm

48
4.7.4. Design Specification Sheet:

1. DESIGN SPECIFICATIONS SHEET

IDENTIFICATION
Name of Equipment decanter
Type Horizontal decanter
Function Density based separation
Number of Units 1
Operation Continuous
Basic Design Data
Pressure 1 atm
Temperature Range 50 deg C
Density of water 1000 Kg/m3
Density of Adipic Acid 1360 kg/m3
Flow rate of Adipic Acid 44.17 kg/hr
Flow rate of water 874.36 kg/hr
Dynamic viscosity of water 0.0414 Ns/m2
Dynamic viscosity of Adipic Acid 0.0005465 Ns/m2
decanter Design
Design Pressure 1 atm
Decanter height 1.5 m
Decanter diameter 0.75 m
Residence time 5 mint
Settling velocity of Adipic Acid 0.00806 m/s
Piping Design
Flowrate 2.519x10^-4 m3/s
Area of Pipe 2.519x10^-4
Velocity of fluid 1 m/s
Diameter of pipe 20 mm
Table 21: Specification Sheet of Decanter

49
Chapter 5

5. INSTRUMENTATION AND CONTROL

5.1. Introduction:
Every chemical plant needs to be monitored by supervisors all the time to avoid any incident
to occur. This is accomplished by instrumentation and control. Designing a complete control
system is the ultimate task of control. It is a complex task to apply a proper control system to
the whole plant but once it is done, it will be as helpful for workers as it increases the safety
measures and standards of any industry. The measurements and manipulations are limited to
small number variables, while the control objectives may not be clearly stated or even known
at the beginning of the control design.
The difficulties are aggravated by the fact that chemical process are largely nonlinear,
imprecisely known, multivariable systems with many interactions. The measurements and
manipulations are limited to small number variables, while the control objectives may not be
clearly stated or even known at the beginning of the control design.
Since we cannot cover all the aspects of plant control within the limits of one chapter, we
focus our attention on describing its essential features. The measurements and manipulations
are limited to small number variables, while the control objectives may not be clearly stated
or even known at the beginning of the control design. A chemical plant is an arrangement of a
number of equipment’s including reactors, absorbers, heat exchangers, dryers, and filters,
distillation columns arranged in a systematic or rational way to produce the desired product.
In addition, we present a rather general methodology for the control system design for a
specific equipment from our plant.
5.2. Incentives for chemical process control:
A chemical plant is an arrangement of a number of equipment’s including reactors, absorbers,
heat exchangers, dryers, and filters, distillation columns arranged in a systematic or rational
way to produce the desired product. However, there are several standards or requirements,
which must be fulfilled to overcome the ever-changing external influences.
These incentives are:
• Safety
• Production specification
• Environmental regulation
• Operational constraints
• Economics
There three general classes of needs that a control system is called on to satisfy:

50
 • Suppressing the influence of external disturbance
• Ensuring the stability of chemical process
• Optimizing the performance of chemical process
5.3. Classification of variables in chemical process:
The variables (flowrates, temperature, pressure, composition etc.) associated with the
chemical process are divided into two types:
Input variables: which denote the effect of surroundings on chemical process
Output variables: which denote the effect of chemical process on the surroundings
5.3.1. Manipulated Variables:
Manipulated variables are those variables that can be changed to control the conditions of any
process. Any one or any combination of following may be the manipulated variables
• Flow rate of the exit product
• Flow rate of feed
• Inlet flow rate of coolant
5.3.2. Loads or Disturbances:
Disturbances are the variables that must be controlled with the help of manipulated variables.
Following are typical disturbances
• Flow rate of product
• Temperature of reactor
• Pressure of reactor
• Temperature of coolant
5.3.3. Hardware for a process control element:
Every control element has the hardware elements including the chemical process, the
measuring instrument or sensors, transducers, transmission lines, the control, final control
element and recording elements.

51
Control scheme on a reactor to control its pressure and temperature

52
Chapter 6

6. HAZOP Analysis
In this chapter we will perform HAZOP analysis on our Heat exchanger. Moreover, we will
also discuss introduction, objectives and methodology of HAZOP analysis. We have also
explained general words and guide words in detail.
6.1. HAZOP Introduction:
A HAZOP analysis i.e. Hazard and operability study is actually efficient and effective way to
analyze and assess the risk potentials of the working of an equipment which we are studying.
This method consistently monitors and takes full account of method of the analysis. This
study analyzes the goals and their impact on the economical action and secure finish of the
plant or the equipment.
Then certain actions are taken by seeing those impacts for the correction purposes. Then the
assessment is done by the team of engineers carrying the HAZOP analysis to find the reason
of deviation from the actual plan of action of the equipment. Albeit, due to rational evaluation
of the equipment, certain failures can be analyzed before the happening of major incident.
6.2. Objectives of HAZOP:
The objectives of HAZOP analysis are given below:
• To define the areas of equipment which could hold great hazard potential
• To assess the likelihood of hazardous or unsafe occurring of event
• To inform the team who is conducting HAZOP about the data available
• To make sure that a rational study is conducted on the areas of high hazardous potentials.
• To take a decision based on rational study that would be appropriate enough that no unlikely
event occur in future.
6.3. HAZOP Analysis methodology:
The HAZOP study will be carried by carrying out the steps given below:
1. Specification of the scope of the study, purpose of the study and its objective should be
described at first. The purpose may include in the form of plant analysis that requires
completion or a survey of the hazards that can be involved in a non-existing unit of a process.
2. Selection of the HAZOP team needed for its study must be made. The leader of the team
has to be skilled in HAZOP and in communal techniques to make easy interactions with the
team. Experts must be made of the team in order cover various aspects of protection,
chemistry of the process, the method involved in the process, the process chemistry involved,
etc.

53
3. Collection of data must be carried out. Following are the list of materials that are usually
required:
• Process’s description
• Process’s flowsheet
• P&I diagrams
• Physical, chemical and toxicological properties of the chemicals involved in the process.
• Specification of equipment and pipes
• Diagrams of control logics of the process
• Layout drawing
• The actions for the operation
• Preservation procedures
• Procedures for crises reaction

6.4. Terms used in HAZOP study:

The terms used in HAZOP study are mentioned below in the table:
Terms Used in HAZOP Interpretations
Process Sections Under defined boundaries the sections of
equipment within deviation are
investigated for process parameters.
Operating steps Analysis carried out by the HAZOP
team that includes distinct actions in a
batch process or a procedure under
analysis.
Intention It gives us the idea that if no deviations
are present in the process, how the plant
will undergo operation.
Guide Words These are words that are simple and are
used to qualify the intended design.
Process Parameter Chemical or physical properties related
to the process under consideration.
These include pressure, flow,
temperature, pH, etc.
Deviations After the application of guide words to
the parameters of the process, various
departures from the design intended that
are observed for each section of the
process, which results in the formation
of the list for the team to review.
Causes The reasons due to which deviations
occur. These causes can be hardware
failures, human errors, unexpected
process states, exterior disruptions, etc.

54
 Consequences Results that occur due to the deviations
in the process. Generally, it assumed by
the team that the safety systems which
are active fail to work.

6.5. Guide words:

These word are simplified keys which tell the team about various ways through which
the occurrence of deviation can happen. Frequently, only small number of
combinations of parameters of process and parameters are used. A list and their
meaning are given as following:

Guide Words Interpretation

None It is an optional word that may not require to
be achieved.
Less The intent of the design undergoes a decline
quantitatively.
More The intent of design undergoes a raise
quantitatively.
Reverse The contradiction of target of design.
Other than The action occurred in other way than
expected.
As well as A quantitative increment
Part of A quantitative reduction

6.6. HAZOP analysis of Heat exchanger:

The HAZOP analysis of the heat exchanger is given below in the table with proper
interpretation of each word.

Guide Word Deviation Causes Consequences Action

High Pressure of shelldischarge valve ofShell side will beInstall high
side shell side closes over-pressurized pressure security
alarm
Low Pressure of shell Tripping ofNo significantNot Applicable
side compressor effect
High Pressure of tubedischarge valve ofTube may rupture Install high
side tube side closes pressure security
alarm
None Flow of coolingFailure of openingProcess FluidInstall
water of inlet valve ofTemperature nottemperature
cooling water. lowered indicators before
accordingly and after the
process fluid line
More Flow of coolingFailure of closingProcess fluidInstall
water of inlet valve oftemperature tootemperature
cooling water low indicators before
and after the
process fluid line

55
Less Flow of coolingLeakages of pipe Process fluidInstallation of
water temperature notflow meter
lowered
accordingly
High Temperature ofThe valve ofTube rupture High Temperature
tube side outlet of tube size security alarm
closes. must be installed
Less Temperature ofCooling waterProcess fluidInstall TIA
tube side high flowrate temperature too
low

56
Chapter 7

7. Cost Estimation
Cost Engineering or Engineering Economics relates to this area of practice, application of
scientific methods and principles for estimating problems, costs control, profitability analysis,
business planning, project management, planning and Scheduling. It is essential that
engineers are aware of the different types of costs during plant construction and operation.
Capital must be provided to cover Both direct and indirect costs.
7.1. Purchased Equipment Cost

Equipment Number of Equipment Purchased Cost $

Heat Exchanger 6 732000
Reactor 1 14000
Decanter 1 30000
Crystallizer 2 480000
Separator 1 1 35000
Separator 2 1 25000
Evaporator 1 112000
Dryer 1 19000
Mixer 1 1053
Total $ 1448053
Table 22:Purchased Equipment cost

Purchased Cost in 2019 = Purchased Cost in 1987 * (cost index in 2019/cost index in 1987)
Cost index in 1987 = 323.8
Cost Index in 2019 = 607.5
Purchased Cost in 2019 = $ 2716776.397
7.2. Total Capital Investment:
T.C.I = F.C.I + WC __________ (1)
7.2.1. Fixed Capital Investment:

F.C.I = Direct cost + In-direct cost

57
Direct Cost
Items % Purchased Equipment Cost Total Cost $
Purchase Equipment 100% 2716776.397
Installation 40% 1086710.559
Instrumentation and Control 14% 380348.6956
Piping 38% 1032375.031
Electricity 15% 407516.4596
Building 25% 679194.0994
Utilities 35% 950871.7391
Safety, Miscellaneous 3% 81503.29192
Land 5% 135838.8199
Total Direct Cost 7471135.093
Table 23: Direct Cost

In-Direct Cost
Items Dependency Total Cost $
Engineering and Supervision 40% of Purchased Cost 1086710.559
Legal Expenses 10% of Direct Cost 747113.5093
Construction and Contractor 5% of Direct Cost 373556.7547
fee
Contigency 8% of Direct Cost 597690.8074
Total Indirect Cost 2805071.63
Table 24: Indirect Cost

Now
F.C.I = $ 10276206.72
Working Capital
31% of Total Capital Investment
WC = 0.31*T.C.I
Putting all the values in Equation (1)
T.C.I = 10276206.72 + 0.31*T.C.I
T.C.I = $ 12089654.97
WC = $ 1813448.245

58
7.3. Total Production Cost
T.P.C = Variable Cost + Fixed Cost + Overhead Charges _________ (2)
7.3.1. Variable Cost
Raw Materials
▪ Cyclohexene
Mass Flowrate = 2660419.3 Kg/yr
Cyclohexene Price = 1.15 $/Kg
Cost of Cyclohexene = 3059482.195 $/Yr
Utilities
▪ Hydrogen Peroxide
Mass Flowrate = 4412401.05 Kg/yr
H2O2 Price = 0.125 $/Kg
Cost of H2O2 = 551550.1313 $/yr
▪ Steam
Mass Flowrate = 1028673.092 Kg/yr
Price = 1 $/Kg
Cost of Steam = 1028673.092 $/yr
▪ Cooling Water
Mass Flowrate = 69072249.6 Kg/yr
Price = 0.0008 $/Kg
Cost of Water = 55257.79968 $/yr
Total Cost of Materials = 4694963.218 $/yr
Items Dependency on T.P.C
Operating labor 0.15
Direct supervision and electrical labor 0.0225
Patent and royalty 0.15
Total 0.3225*TPC
Table 25: Miscellaneous

Total Variable Cost = 4694963.218+0.3225*TPC $/yr

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7.3.2. Fixed Cost

Items Percentage Cost $/yr

Maintenance Cost 7% of FCI 719334.4706
Operating Labor 10% of TPC 0.1*TPC
Supervision 20% of Operating Labor 0.03*TPC
Plant overheads 50% of Operating Labor 0.075*TPC
Capital Charges 10% of FCI 1027620.672
Insurance 1% of FCI 102762.0672
Local Taxes 2% of FCI 205524.1345
Royalities 1% of FCI 102762.0672
Fixed Cost of the Plant 2158003.41+0.205*TPC
Table 26: fixed cost

Direct Production Cost = Variable Cost + Fixed Cost

Direct Production Cost = 6852966.63+0.5275*TPC $/yr
7.3.3. Overhead Charges:
Overhead Charges = 31% of Direct Production Cost
Overhead Charges = 2124419.655+0.1635*TPC $/yr
Now Putting all the values in Equation (2)
T.P.C. = 29053030.05 $/yr
7.4. Production Cost
Production Cost = Annual Production Cost/Annual Production Rate
Annual Production Rate = 4500000 Kg/yr
Production Cost = 6.46 $/kg

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References:
• Vural-Gürsel, I., Wang, Q., Noël, T., Hessel, V., & Tinge, J. T. (2013). Improving energy
efficiency of process of direct adipic acid synthesis in flow using pinch analysis.
Industrial & Engineering Chemistry Research, 52(23), 7827-7835.
• Clark, J. H., & Macquarrie, D. J. (Eds.). (2008). Handbook of green chemistry and
technology. John Wiley & Sons.
• Peñate, I. Q., Lesage, G., Cognet, P., & Poux, M. (2012). Clean synthesis of adipic acid
from cyclohexene in microemulsions with stearyl dimethyl benzyl ammonium chloride as
surfactant: From the laboratory to bench scale. Chemical engineering journal, 200, 357-
364.
• Jiang, H., Gong, H., Yang, Z., Zhang, X., & Sun, Z. (2002). Clean synthesis of adipic acid
by direct oxidation of cyclohexene in the absence of phase transfer agents. Reaction
Kinetics and Catalysis Letters, 75(2), 315-321.
• Gürsel, I. V., Wang, Q., Noël, T., & Hessel, V. (2012). Process-design intensification–
direct synthesis of adipic acid in flow. CHEMICAL ENGINEERING, 29.
• Donald Q. Kern, Process Heat Transfer, 1965, International Edition.
• Musser, M. T. (2000) Adipic Acid Ullmann’s Encyclopedia of Industrial Chemistry,
Wiley-VCH Verlag GmbH & Co. KGaA,
• R.A. Mayer, The 100 Most Important Chemical Compounds, first ed., Greenwood Press,
London, 2007
• Chemical Economics Handbook, 2019
• BCC Research Reports
• Donald E. Garrett, Chemical Engineering Economics
• J. M. Smith, Hendrick C Van Ness, Michael Abbott, Hendrick Van Ness, ‘Introduction to
Chemical Engineering Thermodynamics,’ Sixth Edition.
• Max S. Peters, Klaus D. Timmerhaus, Ronald E. West, ‘Plant Design and Economics for
Chemical Engineers,’ Fifth Edition, University of Colorado.
• Zhang, S. G., Jiang, H., Gong, H., & Sun, Z. L. (2003). Green catalytic oxidation of
cyclohexanone to adipic acid. Petroleum science and technology, 21(1-2), 275-282.

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