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FEEDING STRATEGY OPTIMIZATION

OF NON-LINEAR PROCESSES IN A
SEMI BATCH REACTOR
THESIS SUBMITTED IN PARTIAL FULFILMENT OF
THE REQUIREMENT FOR THE DEGREE OF MASTER
OF CHEMICAL ENGINEERING
AT
JADAVPUR UNIVERSITY
2013
BY
DEBASISH MUKHERJEE
CLASS ROLL NO: 001110302004
REGISTRATION NO: 116773 of 2011-12
EXAMINATION ROLL NO: M4CHE13-04
UNDER THE GUIDANCE OF

PROF. ALAKANANDA MUKHOPADHYAY
http://webcache.googleusercontent.com/search?q=cache:S6fs2-RRwFIJ:jadunivdspace.jdvu.ac.in/bitstream/123456789/28145/1/Acc.%2520No.%25 1/77
DEPARTMENT OF CHEMICAL ENGINEERING
JADAVPUR UNIVERSITY
Page 2
Declaration of Originality and Compliance of Academic Ethics
I hereby declare that this thesis contains literature survey and original research
work by the undersigned candidate, as part of his MASTER OF CHEMICAL
ENGINEERING studies.
All information in this document have been obtained and presented in
accordance with academic rules and ethical conduct.
I also declare that, as required by these rules and conduct, I have fully cited
and referenced all material and result that are not original to this work.
NAME : DEBASISH MUKERJEE
EXAMINATION ROLL NO : M4CHE13-04
THESIS TITLE : FEEDING STRATEGY OPTIMIZATION OF
NON-LINEAR PROCESSES IN A SEMI BATCH
REACTOR
SIGNATURE WITH DATE :
Page 3
CERTIFICATION
This is to certify that the thesis entitled FEEDING STRATEGY OPTIMIZATION OF

NON-LINEAR PROCESSES IN A SEMI BATCH REACTOR, submitted by
Debasish Mukherjee, a student of Chemical Engineering Department, Jadavpur University,
in partial fulfillment of the requirements for the degree of Master of Chemical Engineering is
record of bonafide work which has been conducted under the supervision of Prof.
Alakananda Mukhopadhyay. The contents embodied in the thesis is absolutely his own work
and neither his thesis nor any part of the thesis has been submitted for any degree/ diploma
or any other academic award anywhere before.
----------------------------------------------------- ------------------------------------------------
Prof Alakananda Mukhopadhyay Prof Avijit Bhowal
Project Supervisor Head of Department
Chemical Engg Dept. Chemical Engg Dept.
Jadavpur University Jadavpur University
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Acknowledgement
Firstly, I would like to express my immense pleasure to be a part of the esteemed Jadavpur University to
complete my masters degree in chemical engineering. And being offered this project titled FEEDING
STRATEGY OPTIMIZATION OF NON-LINEAR PROCESSES IN A SEMI BATCH REACTOR under the sincere
guidance of Professor Alakananda Mukherjee bears a great significance to me not only due to the fact that
this project is an integral part of the degree but it is also a great project in terms of its practical scope in the
industry .
The vast experience of Professor Alakananda Mukherjee was really very helpful and handy to have with me
throughout the course of this project and I am thankful to him for his kind support .
I would also like to mention the name of Asst. Professor Somak Jyoti Sahu of Haldia Institute of Technology
who has helped me in every step right from the basics level .
All the lab assistants , librarians laid out their hands whenever I approached , so a big thanks to them too.
Last but not the least , I will thank the Almighty and my parents for their ever enthusiastic support which
has and always will be a lighted kindle for me for the paths to be traversed ahead.
Date .
Debasish Mukherjee
Place
Page 5
CONTENTS
CHAPTER I INTRODUCTION I-1 TO I-6
1.1 INTRODUCTION I-1
1.2 REACTION WITH SO3 I-2
1.3 SULFONATION PROCESS I-3
1.4 ROUTE OF THE REACTION I-4
CHAPTER II PROCESS IDENTIFICATION II-1 TO II-6
2.1 CHEMICAL IDENTITY II-1
2.2 PHYSICAL AND CHEMICAL DATA II-1
2.3 FIRE AND EXPLOSION HAZARD DATA II-1
2.4 REACTIVITY DATA II-2
2.5 HEALTH HAZARD DATA II-2
2.6 PREVENTIVE MEASURES II-3
2.7 ADDITIONAL INFORATIONS AND REFERENCES II-3
2.8 HAZARDS IDENTIFICATION II-4
2.9 PROPERTIES OF LAB, H2SO4, LABSA II-4
2.10 HEAT BALANCE FOR SULFONATION PLANT II-5
CHAPTER III GENERAL SCOPE, PROCESS

III-1 TO III-4
SYNTHESIS AND OBJECTIVE
3.1 OBJECTIVE OF THE PROJECT III-1
3.2 METHODOLOGY III-1
3.3 SCOPE OF APPLICATION III-2
3.4 ECO- FRIENDLY CHARACTERISTICS III-3
3.5 PRESENT SCENARIO III-3
Page 6
CHAPTER IV REVIEW OF LITERATURE IV-1 TO IV-8
4.1 LITERATURE RELATED TO SULFONATION IV-6
REACTION
CHAPTER V MATERIALS USED AND EQUIPMENT V-1 TO V-13

HANDLED
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CHAPTER VI CONTROL MECHANISM VI-1 TO VI-3
6.1 CONTROL OVER THE GENERATION OF HEAT VI-1
6.2 CONTROL OF HEAT ALREADY GENERATED VI-3
CHAPTER VII RESULTS AND DISCUSSION VII-1 TO VII-2
7.1 BATCH MODE REACTION DATA VII-1
7.2 SEMI BATCH MODE REACTION DATA VII-2
CHAPTER VIII OPTIMIZATION OF VITAL PARAMETERS VIII-1 TO VIII-2
8.1 OPTIMIZED H2SO4/LAB RATIO FOR FINAL YIELD VIII-1
8.2 OPTIMIZED BATCH TIME VIII-2
8.3 OPTIMIZATION OF REACTION TEMPERATURE VIII-2
CHAPTER IX CONCLUSION IX-1
NOMENCLATURES
REFERENCES/BIBLIOGRAPHY
Page 8
LIST OF TABLES
Page 9
LIST OF FIGURES
Page 10
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SYNOPSIS
Soap was considered and used as the universal anionic surfactant in both home laundry and
personal care detergent till 1940s. The shortage of nature oils and fats during the Second World War
triggered the development of synthetic surfactants, mainly due to better performance of the latter in hard
water. The success of the replacement, on an industrial scale, has particularly influenced the higher
production of linear alkylbenzene sulfonates since it has resulted in an outstanding improvement of the
production economics and product performances in terms of solubility, foaming ,wetting, detergency and
compatibility with other detergent components. Linear alkylbenzene sulfonates results from the
sulfonation of linear alkylbenzene (LAB) using SO3 as the sulfonating agent. Its specific chemical
composition as well as application and performance depend on two main factors namely the purity of the
LAB and the sulfonation technique used. Molecular weight, carbon chain distribution and its sulfonability
are the main factors for choosing a proper variety of LAB for the process as a raw material. There are
many source of SO3 : 98% conc H2SO4 , oleum, gaseous SO3, chlorosulfuric acid and sulfamic acid. The
reaction between SO3 and the aromatic substrate is an electrophilic substitution reaction with a second
order kinetics.
The present work has dealt with 98% conc. H2SO4 as sulfonating agents, which involves the
stoichiometric formation of water as a byproduct from the reaction. Dilution of still un-reacted sulfuric
acid by this water, causes the progressive loss of the formers reactivity. Feeding H2SO4 continuously
from outside into the reactor would ensure the maintenance of sulfuric acid concentration and hence
sustained reactivity. Along with this, the heat of reaction for the sulfonation reaction, which is as high as
200 kcal/kg of LAB, may lead to insufficient control of temperature in the reaction mixture.
It is proposed to optimize the feeding technique of sulfonation reaction from batch to semi batch
mode using pulsed feeding of H2SO4 through a solenoid valve , thus controlling the generation of exothermic
heat and then providing a jacket on the reactor which automatically shifts between heating and cooling action
depending upon the present temperature of the reactor , ensuring a steady control of reactor temperature at
an optimum of 580C . This results in maximum conversion of LAB to LABSA in a much shorter duration of time.
Page 12
CHAPTER I
INTRODUCTION
Page 13
1.1 INTRODUCTION
In 21st century LABSA is produced by the direct sulfonation reaction of active sulfur tri-oxide and Linear
alkyl Benzene. But in India it is produced by reacting concentrated sulfuric acid with LAB due to
pollution abatement consideration. As it is done in liquid phase in a semi- batch reactor and the reaction is
exothermic in nature, so a proper control strategy is required for quality improvement. The total operation
system can be modeled by achieving detail kinetics (by experimentation). The dynamic characterization
of a process (by mathematical description) that embodies the relationship between input & output of the
process is co-related by the unit operation formula. So process Identification is important for optimization
of the control parameters for a complex process. Here the system is taken as non-isothermal batch reactor
where a homogeneous first order reaction takes place. The dynamic testing is to be done on an open-loop
process. The estimated parameters of the postulated model are used to optimize the control parameters.
The Linearalkylbenzene (LAB) Sulfonic-acids coalition is sponsoring three Linearalkylbenzene
sulfonic-acid materials. This acid is intermediate in the manufacture of linear alkylbenzene sulfonate
(LAS) surfactants, a major cleaning agent in laundry detergents. The Coalition assembled and reviewed
the available public and private toxicological data, and developed an assessment plan for the sponsored
materials. Because of the close structural similarity between LAS and the LAB sulfonic acids, data from
LAS are included to provide supporting information for the category.
The LAB sulfonic acids are highly-water soluble (miscible) and have a relatively low Kow. The
environmental fate data indicate that these chemicals are highly-susceptible to photo and biodegradation.
The aquatic toxicity is consistent across the four chemicals for fish, Daphnia, and algae. The oral
mammalian toxicity is similar and of low concern for all of the chemicals with available data. LAS data
on the chronic aquatic toxicity, repeated dose, reproductive and developmental endpoints do not indicate
any significant areas of concern for the LAB sulfonic acids.
World consumption of LAB in 2001 was estimated at around 2.5 million tons (PETRESA, unpublished
report) which, once sulfonated, was transformed into approximately 3.3 million tons of p-alkyl benzene
sulfonic acid(HLAS), used primarily in detergent and cleaning formulations. Commercial sulfonic acid
contains unsulfonated materials between1% and 1.5% whose major components are sulfones and
unsulfonated LAB in different proportions. The presence of sulfones in HLAS was reported in 1973
[Alamany et.al.] in a work correlating the physical properties of neutralized-HLAS products and their
sulfone content. The quantitative determination of sulfones by high performance liquid chromatography
(HPLC) was described in 1988 [Moreno et.al.], and the relationship between these compounds and the
properties of the neutralized-pastes was confirmed. Similarly, the presence of anhydrides in the sulfonic
I-1
Page 14
acid leaving the sulfonation reactor has been published on several occasions [ Groot et.al.], although their
quantitative determination was only established by liquid chromatography-mass spectroscopy in 1996
[Cohen et.al.].
The formation of the anhydrides and sulfones in the sulfonation reactor has been characterized [Gilbert
et.al] depending on whether the initial pyrosulfonic acid formed reacts with intact LAB or with HLAS.
Other potential reactions with pyrosulfuric acid have been proposed recently [Roberts et.al.].
From the point of view of the sulfonator, the reaction occurring in the reactor are as important as the
mechanism controlling the secondary reaction that takes place in the subsequent process, i.e. aging and
hydrolysis. The purpose of this work was to clarify the kinetics and the stoichiometry of such reactions
and final simulation of the sulfonation reaction in a reactor.
Table 1.1: TYPICAL ALKYL CHAIN COMPOSITION
1.2 REACTION WITH SO3
The various parameters studied in the sulfonic acid at the effluent of the reactor, before the aging step.
The results are represented as a function of the SO3/LAB molar ratio used. There is an optimal SO3/LAB
molar ratio at which a maximum active ingredient is obtained. An increase in the sulfonation ratio above
that value is not reflected in the further increase in active matter. The optimal molar ratio corresponds
with minimal unsulfonated matter production. Although the LAB content in unsulfonated-matter
decreases with increasing sulfonation severity (molar ratio). In other words, the SO3/LAB molar ratio
should be reduced to minimize the production of production of sulfones and anhydrides.
I-2
Page 15
It is generally accepted that the sulfonation reaction of an alkyl aromatic involves an intermediate step in
which pyrosulfonic acid is formed according to following reaction. Pyrosulfonic acid has never been
isolated at the effluent of the commercial-scale sulfonation plant. Irrespectively the mechanism of
formation of pyrosulfonic acid, in the effluent from the sulfonation reaction system there is only sulfonic
acid in high concentration (>95%) and small quantities of sulfuric acid (<2%) and so called unsulfonated
matters, formed by anhydrides, sulfones, and unsulfonated LAB, as well. All these components of
sulfonic acid, including pyrosulfonic acid, are formed in the sulfonation reactor during the short distance
time, usually less than 1minute, of the reacting mixture (SO3+LAB) in the reactor. Therefore, assuming
that pyrosulfonic acid is the main intermediate formed, the other ingredients in the sulfonic acid will be
formed according to the reaction.
1.3 SULFONATION PROCESS
The choice of sulfonating process depends on many factors. One of the most important is the desired
products and their required quality. Some processes are very versatile while others produce only a few
types of products. Each process produces slightly different products. For example, the sulfonic acid
process produces only ammonium sulfates from alcohols or ethoxylated alcohols. Another example is the
presence of a minimum of 8% sulfate in sodium alkyl benzene sulfonates made with oleum. Some
processes such as the air/SO3 process are capable of sulfating or sulfonating a wide variety of feed
stocks and producing excellent quality products from all of them.
A second factor to consider in the choice of sulfonating process is the required production capacity. The
sulfonic acid process is a batch process suitable for production of small quantities of material. The air/SO3
process is a large scale continuous process best suited to 24 hours per day, seven days per week
I-3
Page 16
manufacture of tons per hour of product. The chloro sulfuric acid and oleum processes can be run as
either batch or continuous processes. Reagent cost may have a major impact on choosing a process. The
air/SO3 process has the lowest cost per pound of SO3 reacted while the sulfonic acid process has the
highest. For large scale commodity production, the air/SO3 process clearly has an advantage. However,
for small scale production of a high value specialty product this advantage may be outweighed by other
considerations such as initial equipment cost and the necessity for continuous operation. The process
equipment cost is an important factor to be considered in the choice of a sulfonating process. You must
look at the installed cost of the system, tank and required safety systems. The equipment cost is almost
exactly the inverse of the reagent cost. Here, the air/SO3 process is highest in cost while the simple batch
sulfonic process is lowest. Other processes are intermediate. The final factor to consider in the choice of
sulfonation processes is the cost of waste disposal. The chloro sulfuric acid and oleum sulfonation
processes produce large by-product streams of either hydrochloric acid or sulfuric acid These by-products
must be recovered and sold, or disposed of as a waste. Waste disposal can have a significant impact on
the profitability of these processes, as the necessary equipments are costly and the disposal costs are
high. Table1 1 has shown the trends in sulfonation plants in the United States. The air/SO3 process has
rapidly overtaken the oleum process as the predominate choice. This is the result of several trends. The
first is the waste disposal cost for the spent sulfuric acid from the oleum. The second is the requirement of
many processors to avoid storing a hazardous material such as oleum. The third is that it reduces or
eliminates the sodium sulfate content in detergent. The oleum process adds a large quantity of sulfate to
the products and for many applications this is not acceptable. Finally, the air/SO3 process is capable of
making a broad range of very high quality products.
1.4 ROUTE OF THE REACTION
The LAB is reacted with SO3 or sulfuric acid to make LAB sulfonic acids. The sulfonate group is para to
the alkyl chain attachment on the benzene ring. The LAB sulfonic acids are, in turn, neutralized to the
sodium salts, LAS. This relationship is shown below.
The process adopted for this plant is the liquid liquid rout; where in linear Alkyl Benzene reacts with
Commercial sulfuric acid (98.5% H2SO4) to produce LABSA (Linear Alkyl Benzene Sulfonic Acid). The
reaction is carried out in the medium of excess Sulfonic Acid, which is again separated out and sold or
used as spent acid (75 80 % H2SO4 ). LABSA separated out from spent acid is stored in a separate tank
to be dispatched for sale. LABSA is used for making NSD (Non Soapy Detergent) powder and bar in the
detergent industry.
I-4
Page 17
Stoichiometric reaction:
C6H6 - RCH3 + H2SO4 C6H6SO3H RCH3 + H2O
LAB SULFURIC ACID LABSA WATER
I-5
Page 18
Table 1.2: Structural Representation of Different Sulfonic Acid
I-6
Page 19
CHAPTER II
PROCESS
IDENTIFICATION
Page 20
2. PROPERTIES OF LABSA
2.1 CHEMICAL IDENTITY:
Chemicals classification : Organic surfactant
Chemical Name : Linear Alkyl Benzene Sulfonic Acid
Synonyms : Acid slurry
Trade Name : Sulfonic acid
CAS No. : 68584-22-5
2.2 PHYSICAL AND CHEMICAL DATA:
Specific Gravity (water =1) : 1.03
Physical State : Brown Liquid
Solubility in water at 300c : Miscible with water
pH : Highly acidic in nature
Appearance : Dark Brown Liquid
Odor : Slight pungent
2.3 FIRE AND EXPLOSION HAZARD DATA:
Flammability : - NO
Explosion Sensitivity to static Electricity: - Normal
Hazardous Polymerization : - Yes
Corrosive material : - acidic and corrosive
Flammable Material : - Organic substance
II-1
Page 21
2.4 REACTIVITY DATA:
Chemical stability : Stable at normal Temperature
Reactivity : Can attack readily with alkaline and
also attack metals with liberation of hydrogen.
2.5 HEALTH HAZARD DATA:
Routes of entry : Skin, Ingestion and Eyes.
Effects of exposure/Symptoms : If the
substance has got into the, eyes immediately, wash
out with plenty of water for at least 15 minutes.
Apply dilute sodium bicarbonate solution 2% wipe
out with water then put 2-3 drops of olive oil, seek
medical attention.
Emergency treatment : Remove the contaminate clothing
immediately and wash affected skin with plenty of
water. Seek medical treatment when anyone has
symptoms apparently due to contact with skin or
eyes.
LINEAR ALKYLBENZENE SULFONIC ACID is the largest-volume synthetic anionic surfactant
because of its relatively low cost, good performance, the fact that it can be dried to a stable powder and
the biodegradable environmental friendliness as it has a straight chain. It is produced by the sulfonation of
Linear-alkylbenzene with sulfuric acid other sulfonation alternative reagents are Oleum, diluted sulfur
trioxide, chloro sulfonic acid and sulfonic acid. Surfactants are widely used in the industry needed to
improve contact between polar and non-polar media such as between oil and water or between water and
minerals. It is mainly used to produce the detergent-powder including laundry powders, laundry liquids,
dishwashing liquids and other household cleaners as well as in numerous industrial applications like a
coupling agent and as an emulsifier for agricultural herbicides in emulsion polymerization. Linear alkyl
benzene sulfonic acids (LAS) are anionic surfactants. Linear alkylbenzene sulfonic-acid is a mixture of
benzene sulfonic acid containing Linear-alkyl chains of different lengths (C9: less than 1%, C10: 8 to
16%, C11: 26 to 38%, C12: 26 to 38%, C13: 15 to 27% and longer than C13: less than 2.5%). The
amount of linear alkyl benzene sulfonic acid in the products is 2% and these products are indicated for
II-2
Page 22
post-dipping or teat-spraying of dairy cows. The average dose per teat is assumed to be about 1 ml of the
product, which equals to 80 mg of Linear-alkyl benzene sulfonic acid per cow per milking. Linear-alkyl
benzene sulfonic acids are commonly used as cleaning agents (household and personal care
products). Linear-alkyl benzene sulfonic acid is included as surface active agent in Commission Decision
96/335/EC of 8 May 1996 establishing an inventory and a common nomenclature of ingredients
employed in cosmetic products. The occupational and environmental exposure to Linear-alkyl benzene
sulfonic-acid has been assessed by WHO in 1996: The worldwide consumption of Linear-alkyl
benzenesulfonic-acid in was about 2 million tonnes.
Linear dodecyl benzene sulfonic acid, under the synonym sodium dodecyl benzene sulfonate, has been
included in 1987 on the food additive list of the Food and Drug Administration (FDA) of the United
States of America as a surface active agent in commercial detergents used in washing fruits and
vegetables or to assist in lye peeling these products. The tolerance limit has been set on equal to or less
than 0.2% in wash water.
Areas of Application of LABSA:
Household detergents including laundry powders, laundry liquids, dishwashing liquids and other
household cleaners. Industrial applications of wetting agent, emulsifier for agricultural herbicides and in
polymerization.
2.6 PREVENTIVE MEASURES:
Precautions: Store in a dry place. Protect from We Wear suitable goggles and Protective. Equipments
while handling. Vapor case Irritation of the mucous membrane and Eyes.
2.7 ADDITIONAL INFORMATIONS AND REFERENCES:
Organic acid. Sour taste, ability to make litmus dye turned red to cause other indicator dyes to change to
characteristic colors, ability to react with and dissolve certain metals to form salts, and ability to react
with bases or alkalis to form salts. Corrosive to human tissue.
II-3
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2.8 HAZARDS IDENTIFICATION:
ADVERSE HUMAN HEALTH EFFECTS: The product is a corrosive substance. Contact with the eyes
may cause ocular lesions. Contact with the skin may cause burns. It is seriously irritating to the mucous if
swallowed. The product is harmful if ingested.
ENVIRONMENTAL EFFECTS: The product is not classified as dangerous to environment. The user is
advised to use anyway good work practice and to avoid contamination of environment.
OTHER EFFECTS: The product is a strong acid which reacts exothermally with bases. Dilution with
water produces heat.
2.9 PROPERTIES OF LAB, H2SO4, LABSA:
Inputs :- Per ton of Product
Raw Material :- LAB - 0.740 M.Ton / M.Ton
H2SO4 - 1 M.Ton / M.Ton
Product Name :- LABSA (89%) (Linear Alkyl Benzene Sulfonic Acid),
Product Specifications:
Appearance :- Brown liquid
Active Matter :- 96.0% min
Acid Value :- 180-190
Free Oil :- 1.5% max
Water :- 1.0% max
Color :- Klette 70 max (5% Sol. pH=7, 40mm cell)
Free Sulfuric Acid :- 1.5% max
It is commercially available with the following specifications.
II-4
Page 24
Characteristics
LABSA, % by wt. :- 96 nominal
Colour Klett of 10% :- 100 nominal Solution
Free acid, % max :- 2.0
NDOM, % by wt. Max :- 1.0
2.10 HEAT BALANCE FOR SULFONATION PLANT
Table 2.1: Typical Heat Balance of a sulfonation plant
Qty Unit Remarks
Basis 6000 Kgs( Sulfonic acid 90%)
Heat of Reaction 220 Kcal/Kg. Of LAB
Heat of Dilution of sulfonated mass with

10% water 14000 Kcal/T Of sulfonic acid
Ambient Temperature 35 0C
0
Reaction Temperature 55 C
0
Base Temperature 0 C
FEED
LAB 4080 Kgs
Sulfuric acid 6360 Kgs
Water 720 Kgs
Total Sulfonated mass 11160 Kgs
HEAT IN
LAB 4080*0.45*35 64260 Kcal
Sulfuric acid 6360*0.45*35 100170 Kcal
II-5
Page 25
Heat of reaction 220*4080 897600 Kcal
Total Heat In 1062030 Kcal
HEAT OUT
Suphonated mass 11160*0.5*55 306900 Kcal
Cooling Water required with 50 C T.Diff. (1062030-306900)/5 151026 Kg
Cooling Water required /Hr (For 4Hrs

reaction cycle) 151026/4 37756.5 Kg/hr
Volumetric flow rate of Cooling water 38 m3/hr
Heat of dilution (For dilution cycle of one

hr.) 14000*6 84000 Kcal
Water required to maintain temperature of

55degC with cooling water temp. rise of
5degC
84000/5 16800 Kg
Volumetric flow rate of water 17 m3/hr
Max.Load on cooling tower in T 250
For 3 reactors Max., requirement of

cooling water 38m3/hr*3 114 m3/hr
Existing
Cooling
Tower is
Just
Sufficient
Actual capacity provided 100m3/hr
6 6C
Actual Temp Rise expected by using
100m3/hr Cooling water
Capacity of Chiller TR required to 28 One more

maintain temp @55c+/- 2C for 3 Chiller unit
Reactors of similar
capacity
required
Actual Capacity TR available 16
II-6
Page 26
CHAPTER III
GENERAL SCOPE
PROCESS SYNTHESIS
AND
OBJECTIVE
Page 27
3.1 OBJECTIVE OF THE PROJECT:
In the recent work, it is aimed to optimize the feeding of the sulfonation reaction using H2SO4 as the
sulfonating agent and adding it in a pulse feed manner to minimize heat generation and further provide heating
and cooling effect through a reactor jacket to ensure proper maintenance of reactor temperature for maximum
conversion of LAB in minimum time.
The detailed objectives of the whole work are as follows;
1. To optimize the feed flow of the particular sulfonation reaction.
2. To identify the key process parameters.
3. To apply feed forward control in the reactor .
4. To make the reaction process industry-friendly and cost effective to encourage entrepreneurs to implement it .
5. To optimize the batch time.
6. To determine a strategy for improving the product quality.
3.2 METHODOLOGY:
The experimental investigation to study the reaction performance and controllability of the semi batch
reactor will be conducted in the following manner:
1. The semi batch reactor needs to be modified as per the design (with valve system).
2. About 10 liters of concentrated sulfuric acid need to be stored in the HDPE (Fig 5.4) tank as overhead
reservoir.
3. The circulation pump is started, to maintain the flow rate of sulfuric acid.
4. Molar ratio of sulfuric acid and LAB is maintain at 2.0
5. Bath heater is switched on to raise the temperature of the reaction system as the reaction starts at a
higher value than room temperature.
6. A chilled water supply is ready for 2nd phase operation.
III-1
Page 28
7. When the reaction is started at specified temperature the bath heater is switched off and chilled water
supply is stated to maintain the reaction temperature at different points to study the kinetics.
8. Reaction sample is collected every five minutes and simultaneously titrated using 0.5 (N) NaOH
solution.
9. The amount of reacted alkali, that is equal to the amount of excess sulfuric acid, is determined by
titration of the liquid samples and the amount from the titration value gives how much LABSA is
produced.
9. The steps 2, 3, 5, 6, 7, 8, 9 are repeated for reactor temperature 450C, 500C, 550C, 600C, 620C, 650C.
10. Steps 1 to 9 is repeated with mole ratios at 1.2, 15, 1.8
11. Dynamic response of the reactor would be determined with the same experimental setup as in Fig.
The step and pulse type disturbances are to be introduced through sulfuric acid flow rate. Corresponding
responses are recorded by the pH measurement. Response data would be obtained for different values of
(i) flow rate, (ii) temperature.
3.3 SCOPE OF APPLICATION:
Linear alkyl benzene sulfonic acids (LABSA) are anionic surfactants. Surfactants are widely used
in the industry needed to improve contact between polar and non-polar media such as between oil and
water or between water and minerals.
LABSA is used for making NSD (Non Soapy Detergent) powder and bar in the detergent
industry. Industrial applications include raw material for detergent, as coupling agent and as an emulsifier
for agricultural herbicides and in polymerization. Detergents refer to the household detergents including
laundry powders, laundry liquids, dishwashing liquids and other household cleaners.
III-2
Page 29
3.4 ECO- FRIENDLY CHARACTERISTICS:
LAS (or LABSA) have been studied extensively both in the laboratory and under more realistic
conditions. Following environmentalfriendly features are associated:
1. LABSA is highly water soluble.
2. Highly susceptible to biodegradation.
3. Not a matter of concern for oral mammalian and aquatic toxicity.
Moreover, they biodegrade in
1. surface water in 1 - 2 days
2. aerobic sediments in 1 - 3 days, &
3. marine systems in 5 - 10 days.
3.5 PRESENT SCENARIO:
Today, LABSA is produced by the direct sulfonation reaction of active sulfur tri-oxide and Linear
alkyl Benzene. But in India, it is produced by reacting concentrated sulfuric acid with LAB due to
pollution abatement rule. Speaking of producers; from western side, some of renowned manufacturers
like CV Pacific Indochem, Advance Surfactants India Ltd., etc. are producing LABSA. But, TATA
Chemicals Ltd. is the only company from the eastern side that produces LABSA for surf excel
production.
As it is done in liquid phase in a semi- batch reactor and the reaction is exothermic in nature, so a
proper control strategy is required for quality improvement.
The total operation system can be modeled by achieving detail kinetics (by experimentation). The
dynamic characterization of a process (by mathematical description) that embodies the relationship
between i/p & o/p of the process is co-related by the unit operation formula. So process Identification is
important for optimization of the control parameters for a complex process.
III-3
Page 30
Here the system is taken as non-isothermal batch reactor where a homogeneous first order
reaction takes place. The dynamic testing is to be done on an open-loop process. The estimated
parameters of the postulated model are used to optimize the control parameters.
The Linear Alkylbenzene (LAB) Sulfonic Acids Coalition (Coalition) is sponsoring three linear
alkylbenzene sulfonic acid materials. These acids are intermediates in the manufacture of linear
alkylbenzene sulfonate (LAS) surfactants, a major cleaning agent in laundry detergents.
The Coalition assembled and reviewed the available public and private toxicological data, and
developed an assessment plan for the sponsored materials. Because of the close structural similarity
between LAS and the LAB sulfonic acids, data from LAS are included to provide supporting information
for the category.
The LAB sulfonic acids are highly water soluble (miscible) and have a relatively low Kow. The
environmental fate data indicate that these chemicals are highly susceptible to photo-and biodegradation.
The acute aquatic toxicity is consistent across the four chemicals for fish, Daphnia, and algae.
The acute oral mammalian toxicity is similar and of low concern for all of the chemicals with available
data. LAS data on the chronic aquatic toxicity, repeated dose, reproductive and developmental endpoints
do not indicate any significant areas of concern for the LAB sulfonic acids.
III-4
Page 31
CHAPTER IV
REVIEW OF
LITERATURE
Page 32
REVIEW OF LITERATURE
V-1
Page 33
IV-2
Page 34
IV-3
Page 35
IV-4
Page 36
Sl
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formation. March 2000,
Pages 141148
e A new method for
ab determination of linear
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h d Trace determination of linear alkylbenzene sulfonates
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aman ultrasound-assisted dispersive ultrasound-assisted dispersive Issue 8, 2012,
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M response surface methodology (IL-USA-DLLME) coupled 2272-2277
ajidozorgzadeh
A with spectrophotometry
M B
detection.
IV-5
Page 37
4.1 LITERATURE RELATED TO SULFONATION REACTION:
Selective set of Abstracts of important papers are given below:
1. J.E. Kircher, E.L.Miller and P.E. Geiser, Industrial and Engineering Chemistry, Vol-46, No-9, pp.
1925-1930, 1954
This description of commercial detergent alkylates includes physical properties such as molecular weight,
boiling range, and color and their effects on sulfonation and the finished sulfonate. The discussion of the
sulfonation procedure gives the strength of acids used in the sulfonation reaction (from 98% sulfuric acid
to sulfur tri oxide); physical data for sulfonation with 20% Oleum and with 100% sulfuric acid; and heat
transfer data, viscosities and specific gravities of sulfonic acids. Variables are weight ratios of acid
alkylate, temperatures adhered to during sulfonation and aging times and temperatures of the sulfonation
mass. Spent acid separation variables include settling time and temperature and dilution of the reaction
mass.
2. Gary R. Johnson and Billy L. Crynes, Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1,
pp.6-14, 1974
The manufacture of detergents is an interesting and highly specialized industry in the United States. At
the present time the most common raw material for formulation of household detergents is linear
alkylbenzene. The alkylbenzene is sulfonated with sulfur trioxide to make the sulfonic acid. Following
this, the sulfonic acid is then neutralized and mixed with other ingredients to make the final detergent.
Sulfur trioxide is an extremely reactive compound, being an oxidizing as well as a sulfonating agent. The
sulfonation reaction rate is instantaneous and exothermic; the heat of reaction is about 900 Btu/lb of SO3
reacted. As a result liquid SO3 cannot be added directly to the organic material to be sulfonated because
of safety and product degradation problems. Instead SO3 is commonly vaporized and diluted with dry air.
Thin-film sulfonation reactors are becoming more widely used in the detergent industry as a means of
directly combining sulfur trioxide with organic materials. The reaction however is highly exothermic and
can under certain conditions produce degradation of the product. Presented is an engineering model for
predicting the longitudinal temperature and conversion profiles of the organic liquid film during its travel
along the reactor tube. The model then predicts product quality under various operating conditions.
Results show that a large portion of the total conversion occurs in the first few inches of the reactor length
producing a maximum liquid film temperature in that region. Reactor outlet temperatures do not give a
clear indication of the magnitude of the front end temperature peak. Variables such as loading, inert gas
rate, cooling water temperature, and reactor diameter substantially affected the liquid film temperature
profile.
IV-6
Page 38
3. David W. Roberts, Organic Process Research & Development, Vol-2, pp.194-202, 1998
Sulfonation is the predominant route to manufacturing of anionic surfactants other than soap. The
fundamentals of sulfonation technology have been developed largely in the detergents industry, but many
of the more recent advances have been equally driven by quality requirements for surfactants to be used
in personal products and cosmetics applications. This paper presents an overview of reactor technology
and reaction chemistry for surfactant manufacture via sulfonation with sulfur trioxide. The manufacture of
surfactants derived from linear alkylbenzenes, primary alcohols, ethoxylated alcohols, and alpha olefins is
described.
4. J. Gutierrez-Gonzalez, C. Mans-Teixido, and J. Costa-Lopez, Ind. Eng. Chem. Res., Vol-27,
pp.1701-1707, 1988
The sulfonation or sulfation reaction is generally utilized for the production of detergents. By means of
this reaction, hydrophilic groups-CS0- or COSOs--are introduced in organic compounds with
hydrophobic chains. The sulfonation agent SO3 is one of the most utilized because it has some advantages
with regard to other agents: sulfuric acid or Oleum. Two of these advantages are that it reacts
stoichiometrically and without secondary products. However, SO3 reaction with organic compounds is
very exothermic, -1.68 X 10^5 J/mol of SO3, for the sulfonation of Dodecylbenzene and requires good
refrigeration to avoid the degradation of the products. A mathematical model of a process in which an
exothermic, second-order reaction takes place in a falling film reactor was developed. This model is
applicable to a process in which any step, liquid mass transfer, reaction rate, or gas mass transfer, can
affect the process rate. The model includes a turbulent diffusivity term for the liquid mass transfer, valid
through the entire liquid film. The mathematical model predicts conversions and interfacial temperatures
as the most important variables for product yields and product quality. Its validity was proved by means
of experimental sulfonation of Dodecylbenzene. This model could be applicable to any process that takes
place in a falling film reactor.
5. B.Dabir, M.R.Iazi and H. Davoudirad, Chemical Engineering Science, Vol. 51, No. 11,
pp. 2553--2558, 1996
Falling film reactors are being widely used for exothermic gas-liquid reactions such as sulfonation or
chlorination. In the chemical industry, falling fill reactors are used in detergent and wetting/dispersing
agents manufacturing plants. Sulfonation of Dodecylbenzene (DDB) or linear alkyl-benzene (LAB) by
sulfur trioxide (SO3) gas is the best examples of reactions occurring in these industries. An improved
mathematical model for falling film reactors is presented. Effects of liquid film turbulence, gas phase heat
and mass transfer resistances, gas-liquid interfacial drag, exothermic chemical reaction and heat transfer
IV-7
Page 39
within the system, as well as volatility of liquid film are considered. The model predicts liquid phase
chemical conversions and the interracial temperatures along the reactor length. Model predictions agreed
well with data from both laboratory and industrial scale reactors.
6. A. Moreno, C. Bengoechea, J. Bravo, and J.L. Berna, Journal of Surfactants and Detergents, Vol-6,
No-2, pp. 137-142, 2003
Modern industrial sulfonation of linear alkylbenzene (LAB) in falling film reactors produces
p-alkylbenzene sulfonic acid (HLAS), which is usually neutralized with caustic soda (NaOH) and used in
detergent formulations. During the sulfonation process, other products such as anhydrides and
sulfones are also formed. Four reactions are proposed to occur during aging and hydrolysis. As a
consequence, approximately 25% of sulfones and 75% of unreacted LAB are removed during aging and
are transformed into additional active matter. Anhydrides are completely eliminated during hydrolysis.
On the other hand, sulfones formed during the process are difficult to remove once formed. The goal of
this work was to optimize the various operating conditions of the sulfonation process and to understand
the various secondary reactions that occur therein so as to obtain a maximal active ingredient
concentration in the final sulfonated product and a minimum of unsulfonated matter. Formation of
sulfones can be minimized by using an SO3/LAB molar ratio slightly lower than the theoretical optimum.
IV-8
Page 40
CHAPTER V
MATERIALS USED
AND
EQUIPMENTS HANDLED
Page 41
EQUIPMENTS AND CHEMICALS HANDLED
The various chemicals and equipments handled during the experimentation and subsequent
testing are described below
5.1 EQUIPMENTS REQUIRED FOR STUDY OF REACTION KINETICS:
1. Storage Tanks
2. Reactors with Accessories
3. Circulation Pumps
4. Filters for LABSA
5. Hydrolyser
6. Reactor Cooling Arrangements
7. Pumps
8. Piping and Valves
9. Instruments Panel
10. Product Storage Tanks
11. Exhaust Gas Cleaning
V-1
Page 42
5.2 SUBSTANCE:
TRADE NAME: LABSA
APPLICATION: Intermediary for the production of Detergent.
5.3 INTERMEDIATE FOR DETERGENT MANUFACTURING:
Detergents use a synthetic surfactant in place of the metal fatty acid salts used in soaps. They are made
both in powder and liquid form, and sold as laundry powders, hard surface cleansers, dish washing
liquids, fabric conditioners etc. Most detergents have soap in their mixture of ingredients, but it usually
functions more as a foam depressant than as a surfactant.
Table 5.1: Ingredients of Detergent Base Powder
V-2
Page 43
5.4 DETAILS OF EXPERIMENTATION:
The process can be divided into the following steps (Fig.1) and it is arried ut batch-wise.
- In-house production of sulfuric acid
- Sulfonation of LAB (Step : 1)
- Spent acid generation (Step : 2)
- Separation of sulfonic acid from spent acid (Step : 3)
Step 1 : Sulfonation of LAB
Sulfonation of hydrocarbons especially at benzene ring is difficult due to its non polar nature. Sulfonation
of LAB with concentrated sulfuric acid is achieved using sulfuric acid more than three times of the
stoichiometric requirement. One mole of hydrocarbon having homolog distribution of C10 to C13 (average
molecular weight: 327) undergoes sulfonation reaction with presence of three moles of sulfuric acid to
over 98% sulfonation, leaving two moles of sulfuric acid as spent acid in the reactor. Sulfonation is
carried out under controlled temperature of 550C to 650C and takes around 6 hours for the completion of
reaction.
R (C10 to C13) R
+ H2O + 2 H2SO4
+ 3 H2SO4
(Spent Acid)
SO3H
Step 2 : Spent acid generation
Reaction is ceased with dosing of chilled water in the reactor and thereby excess concentrated sulfuric
is converted to spent acid having around 70% strength. It remains mixed with sulfonic acid (LABSA).
During the reaction, small part of hydrocarbon is carbonized with concentrated sulfuric acid, resulting
in black spent sulfuric (strength 70%).
V-3
Page 44
Step 3 : Separation of Sulfonic acid
The mixture sulfuric acid and spent acid is drained into the separator. Sulfuric acid lighter having
specific-gravity around 0.9 ~ 1.0, where as that of spent acid is in the order of 1.65 ~ 1.75. Due to
differential density, spent acid gets accumulated at the bottom of the separator and is finally discharged
into the spent-acid storage tank. The upper layer LAB sulfonic acid is then drained to sulfonic acid storage
tank. Spent acid is, therefore, an inevitable by-product, unavoidable and a technological necessity. Spent
acid is then transferred to single super-phosphate plant for captive consumption. Linear-alkylbenzene gets
fully utilized in the manufacturing of the sulfonic acid and it is not contained in the spent sulfuric acid.
5.5 PRODUCTION PROCEDURE OF LABSA IN INDUSTRY:-
At first LAB taken in a semi-batch reactor, it heated up to 400 c. After that H2SO4 is added drop-wise in
this reactor. Agitation has done in this system. The agitator speed is maintained at certain rpm(70-80). In
the system some cooling water arrangement is there. This cooling-water is cooled by cooling coil. The
cooling coil is fixed in the reactor. Cooling water temperature maintained at 35-400c. Because when acid
has used in the reactor then the temperature is increased certainly. Acid has used in a limited time period.
The flow rate rise of acid is maintained. When acid feeding is complete then cooling-water is used. The
reaction temperature maintains at about 600c. If the reaction temperature is increased, the product quality
is deteriorated. That means the product colour is more than the required colour i.e. risen of market value
of the product is less. For that reason the reaction temperature is maintained. When the acid addition is
completed the agitated speed is increased, and the concentration of the mixture is increased. The reaction
is going on 5-6 hr. The mixture is then settled in the reactor without any agitator. The settling time of the
mixture is about 4-5 hr. Then it is kept at about 2 hr to phase separation. The upper and the lower phase
are LABSA and spent-acid phase respectively. The bottom phase is drained out from the reactor and take
LABSA from upper-phase of the reactor. The spent-acid is a mixture of H2SO4, water and some amount
of un-reacted LAB. In industry LAB is used 3.6 ton., H2SO4 is used 7.5 ton and 750kg water per batch.
The batch time is about 5-6 hr. the spent-acid is separated out and sends to other industries. Some amount
of the spent-acid is recycled in the reaction vessel or the reactor. Here the H2SO4 concentration is
98.98% and LAB has reacted with H2SO4 and produced LABSA. The LABSA production is going on
batch-wise in the industry. The LABSA production rate is 4batches per day in the industry like TCL. The
concentration of the LABSA is about 85-88% in the final product.
V-4
Page 45
5.6 PRODUCTION PROCEDURE OF LABSA IN LABORATORY:-
In laboratory scale experiment small quantity is used. Magnetic starrier is used as an agitator. The
agitated speed is maintained at 70-80 rpm. The feeding system is divided into three parts:-
i) LAB and H2SO4 is mixed at a same time.
ii) First the LAB is heated up to 400C and then H2SO4 add certainly.
iii) LAB is heated up to 400C and then H2SO4 acid add drop wise at a fixed flow rate.
Three procedures are maintained at a certain temperature. Here the magnetic starrier is used with heating
coil.. The duration of experiment at about 4-5 hr.
1ST EXPERIMENTAL PROCEDURE:-
First LAB is taken 930.3 gm. and H2SO4 is taken 200 gm. The acid and LAB are taken in 500 ml beaker
and the mixture is heated up in magnetic stirrer with heating arrangement. Then the temperature of the
mixture is risen. The temperature of the mixture is maintained at 600c. If the temperature of the
beaker has increased above the 600c some cooling arrangement has provided to cool the temperature and
it at 600c. The magnetic starrier is used to stirring the mixture. The starrier speed is maintained at 70-80
rpm. Then the reaction is going on. Then after some time interval 0.3-0.5 gm of sample has collected from
the reactor mixture and is titrated with the help of hyamine solution. Also the sample is collected at the
end of reaction. Then the mixture is settled down at the room temperature. The settling time is 4-5 hr. then
the mixture is divided into two phases. The upper phase is LABSA and the bottom phase is spent-acid.
The colour of LABSA phase is light brown and that of the spent-acid phase is dark-brown. Some amount
of LABSA is taken and titrated. From the titrated value calculate the percentage of LABSA conversion in
the final product.
2ND EXPERIMENTAL PROCEDURE:-
LAB is taken 93.06 gm and H2SO4 is taken 204 gm in a 500 ml beaker. First LAB is kept in the beaker
and it is heated upto 400C with the help of magnetic stirrer with heating arrangement. The stirring speed is
maintaining 70-80 rpm. The reaction time is about 4 hr. Reaction temperature is maintained at 550c. The
cooling arrangement is needed to maintain the temperature. The reaction started then the sample is
collected in certain interval of time are 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, 120,
140, 160, 180, 200, 230, 260 min. Collected sample is titrated and calculate the %conversion of the
LABSA. Then the mixture was cooled down and settled. The settling time about 4-5 hr. The mixture is
V-5
Page 46
separated and the upper phase is collected and titrated. Then calculate the final percentage conversion of
the LABSA. The percent conversion of LABSA is about 86%. The final product colour is light brown and
the spent acid colour is brown. The time vs. concentration is plotted to find the rate constant.
3RD EXPERIMENTAL PROCEDURE:-
In this procedure one special type of beaker is used. This beaker volume is one litter. Then the beaker is
filled up with concentrated H2SO4. At the lower portion of the beaker was fitted in a pipeline and pinch
coke is used to maintain the flow rate of acid. At a specific flow rate acid is added to the system. The flow
rate of acid is maintained at 0.0535 ml/sec. LAB is taken 100 gm and heated up to 400c with continuous
stirring. When the reactant temperature riches 400c then H2SO4 is added drop-wise at the fixed flow rate.
After 30 min the samples were collected in a time of interval. The reaction temperature is maintained at
55-600c. When the reaction temperature was increased and it crossed the set point then cooling has
started. The sample were collected in a time interval of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 80,
120, 160, 180, 200, 220, 240, 260 , 290, 320 min then collected samples were titrated. The 214.18 gm H-
2SO4 is added and after 30min the H2SO4 addition has stopped. Mixture has stirred by the magnetic
starrier. The stirring speed has maintained at 70-80 rpm. The collected samples were titrated in
the procedure discussed. Then time and concentration value is plotted to determine reaction rate-constant.
The reaction time was 4 hr. Then the reaction mixture was settled down. The upper and lower
phases were LABSA and spent-acid respectively.
V-6
Page 47
Fig5.1: Schematic Diagram of the Reactor Set up
V-7
Page 48
5.7 TEST OF SULFONIC ACID CONTENT IN LABSA:
APPLICATION: SULFONIC ACID
PRINCIPLE:
The anionic active matter after neutralisation is determine by titration with (0.004M) Hyamine
using Methylene Blue as indicator and calculate as active matter.
CHEMICALS:
1. Hyamine 1622, E.MERCK . Part no :- 1922233F 0.004(M)
2. Chloroform. Analytical reagent.
3. Methylene Blue solution: Dissolve 0.5 gm of BDH standard stain Methylene Blue in
100 DM water . To 5 ml of this solution, add 50 gm anhydrous Sodium Sulfate
(dissolved in water). Add 120 ml of 2N Sulfuric acid and dilute to 1000 ml with
with D.M water.
APPARATUS:
1. 10 ml pipette.
2. 100 ml graduated measuring cylinder with glass stopper.
PROCEDURE:
1. Weight about 0.3-0.5gm of the representative sample in a 500 ml volumetric flask.
2. Add about 150 ml of DM water dissolve the sulfonic acid sample by swirling then add a few
drop of phenolphthalein indicator solution.
3. Neutralize this solution with 5(N) NaOH solution to pink colour and make up to the mark.
4. Pipette 10 ml of this dilute solution into 100 ml stopper cylinder.
5. Add 25 ml methylene blue solution and 15 ml chloroform.
6. Replace the stopper and shake; the upper aqueous phase will be almost colourless, and the
chloroform phase dark blue.
7. Add 2 ml Hyamine solution from a burette replace the stopper and shake for about 10
seconds.
V-8
Page 49
8. Continue making 2 ml addition of Hyamine solution, shaking for 10 seconds after each
addition, until the blue colour begins to appear in the aqueous phase.
9. Compare the colour of the two phases after each addition.
10. As the end point is approached, add progressively smaller volumes of hyamine solution and
shake for 30 seconds, after each addition, allow to settle and judge the colour intensity f the
phases.
11. The end point is obtained when the colour intensity of the chloroform phase. The addition of
a further drop of Hyamine solution will develop a paler tinge in the chloroform layer.
CALCULATION :
% LABSA = V X 0.004 X 500/10 X 100/W X 320 X 1/1000
Where V is the volume in ml of Hyamine consumed for titration.
W is the weight in gms of the sulfonic acid taken for analysis.
320 is the molecular wt of sulfonic acid taken for analysis.
5.8 TEST OF SULFURIC ACID CONTENT IN LABSA
APPLICATION: SULFURIC ACID
PRINCIPLE:
The Sulfuric acid content in LABSA is determined by titration of the neutralised sulfonic acid with
Lead Nitrate solution using Dithiozone indicator and calculated the concentration of sulfuric acid.
REAGENTS:
Nitric Acid = 2(M) solution
Acetic Acid= 20 % (v / v) solution
Lead Nitrate= 0.01M solution accurately standardised. Dissolve 3.31 g of Pb(NO3)2 analytical
grade, in 1000 ml of distilled water
Sodium Sulfate= 0.01 solution Dissolve accurately weighed 1.4206 g of anhydrous Sodium
Sulfate dried to constant weight at 110 C., in distilled water. Transfer to 1000 ml graduated flask,
dilute to the mark and mix.
V-9
Page 50
Bromophenol Blue = 0.1 % (w/v) in 96 % (v / v) ethanol
Dithiosone = 0.05 % (w / v) in acetone, prepared fresh daily.
Acetone & Isopropyl alcohol Analytical reagent
APPARATUS:
- 50 ml burette.
- 250 ml conical flux
PROCEDURE:
1. Weight 0.4 - 0.5 gm of LABSA sample in a 250 ml conical flask.
2. Dilute with 50ml of DM water, add 3-4 drops Phenolphthalein indicator & neutralize with 5
(N) NaOH. Then add a 3-4 drops of BromoPhenol Blue indicator solution.
3. Neutralise until the colour to just yellow by adding drop wise 2(M) Nitric acid solution.
4. Add 2 ml acetic acid solution, 50 ml acetone, 50 ml isopropanol and 2 ml dithiozone solution.
5. Titrate the mixture with Lead Nitrate solution while stirring with a magnetic stirrer until the
colour changes from emerald green to reddish purple.
STANDARDIZATION OF LEAD NITRATE SOLUTION:
1. Pipette 25 ml of the sodium sulfate solution in a 250 ml conical flask.
2. Proceed as described in steps 3-4.
3. Calculate the actual concentration of the Lead Nitrate solution in mol / L from the volume
used for titration.
CALCULATION:
%H2SO4 = V X 0.098 X f X 100/W
Where W is the wt in gms taken for titration.
"f" is the factor of Leased Nitrate solution.
V-10
Page 51
5.9 TEST OF NON DETERGENT ORGANIC MATTER:
The NDOM content of sulfonic acid produced by SO3 - air sulfonation of alkylbenzene is likely to
alter during storage between sampling and testing.
PRINCIPLE:
The NDOM is extracted with petroleum ether from a solution of the neutralised crude sulfonic
acid in 50 % ethanol.
REAGENTS:
Ethanol=96% v/v aqueous solution
Ethanol=50% v/v aqueous solution
Petroleum Ether=Boiling range 40 to 60o c
Acetone=Dry
Sodium Hydroxide=1 N solution
The solvent must leave no residue after evaporation.
PROCEDURE:
1. Weigh accurately 5 -10 g of representative sample containing about 50 - 100 mg NDOM
in a beaker.
2. Add 20 ml water and dissolve by warming.
3. Titrate the solution with 1N sodium hydroxide using phenolphthalein as an indicator
until permanent pink colour appears.
4. Add 1 ml excess and note the volume (v) used.
5. Transfer the solution and the washings quantitatively to a 500 ml separating
funnel. Wash the beaker with small volumes of water using in all (79 - V) ml.Transfer
each washing to the funnel.
6. Add 75 ml of 96 % ethanol and swirl gently to mix.
7. Add 75 ml of petroleum ether stopper the funnel and shake for about 1 minute.
V-11
Page 52
8. Stop shaking at regular intervals and open the stop cock of the funnel to release the
pressure.
9. Allow the phases to separate and run the aqueous ethanolic phase into another separating
funnel.
10. Extract ethanolic aqueous phase with 75 ml petroleum ether as above and transfer the
ether in the first separating funnel.
11. Wash petroleum ether extract twice with 50 ml of 50 % ethanol.
12. Allow the phases to separate after each wash and run off the lower aqueous phase
completely.
13. Filter the petroleum ether extract through sodium sulfate in a tared flask.
14. Evaporate off the petroleum ether carefully, add 5 ml acetone.
15. evaporate off the acetone on water bath.
16. Pass dry air into the flask for 2 mins.
17. Place the flask in an oven at 105 C for 15 minutes, cool in a desiccators and weigh.
CALCULATION:
Let, Weight (in g) of the sample=W
Weight (in g) of NDOM= W1
w1 100
NDOM
w
V-12
Page 53
5.10 TESTING COLOUR OF SULFONIC ACID
PRINCIPLE:
Colour of 10 % solution of Sulfonic acid (as is basis) is measured using a photo electric
colorimeter fitted with a No. 42 filter.
REAGENTS:
Ethanol=95%
APPARATUS:
Colorimeter = Photo electric colorimeter-Test Tube Mode No. 42 Blue
Filter = Filter
Cell = 1.5 cm diameter glass tube
PROCEDURE:
1. Weigh 5 g of sulfonic acid (after mixing well) in a 150 ml beaker.
2. Add 45 ml of 95 % ethanol.
3. Stir well to dissolve.
4. Fill the cell with ethanol and place in the instrument. Zero the instrument using the zero
adjust knob.
5. Replace the blank solution with the solution of the sample. Turn the scale knob, until the
pointer has been brought back to the zero position on the scale.
6. Record the scale reading, noting also the filter No., concentration, and path length used..
V-13
Page 54
Page 55
CONTROL MECHANISM INVOLVED IN THE SYSTEM
The key feature of the control mechanism used in the project is TEMPERATURE CONTROL
THROUGH FEED CONTROL
Firstly, there is CONTROL OVER THE GENERATION OF HEAT
Secondly, there is CONTROL OF HEAT ALREADY GENERATED
Both this parts are described as below:
6.1 CONTROL OVER THE GENERATION OF HEAT
As we know, that the sulphonation reaction is exothermic, so if we control the input of sulphuric acid into the
reactor, the generation of exothermic heat will be automatically controlled. Now, for that purpose, we have
used a solenoid valve in the acid flow pipeline prior to its entry into the reactor. The valve is controlled by a
PID controller, which takes the reactor temperature as its input, and calculates through a simple quadratic
formula the on-time of the valve, depending upon which the calculated amount of acid goes into the reactor
preventing any extra heat generation.
The off-time is of the valve is also set in a similar fashion, to allow the heat to be dissipated uniformly,
and the valve waits for its next on-time for opening and subsequent acid input into the system.
This type of control is nothing but PULSE WIDTH MODULATION, where the amount of acid
input into the system is varied just by increasing or decreasing the width of on-time and off-time of the
solenoid valve. The total sum of on-time and off-time of the valve constitutes one complete cycle. The flow of
0
acid is completely stopped for sometime if the temperature reaches beyond 62 C to prevent degradation and
blackening of LABSA. A simple diagram will illustrate the acid feed into the reactor:
Fig 6.1
VI-1
Page 56
In this regard, first a calibration curve is obtained which depicts the nature of response of the valve with the
deviation of on-time and subsequently the effect on the amount of acid going into the reactor.
The data obtained is tabulated as below: Table 6.1
volume
total on off time
collected
36 5 49.9
48 5 78.2
60 5 93.5
72 5 108.8
84 5 120.2
96 5 136.3
108 5 170
120 5 181
180 5 257
The graphical representation of the above data with total on time on the x-axis and volume of sulphuric acid
collected on the y-axis is shown below:
300
y = 1.423x + 5.618
250
200
150
Series1
100
50
0
0 50 100 150 200
Fig 6.2
This calibration curve is used to calculate the amount of acid that will go into the reactor through the valve for
a particular value of on-time.
VI-2
Page 57
6.2 CONTROL OF HEAT ALREADY GENERATED
The control of heat already generated is done primarily by the agitator provided inside the reactor which helps
in dissipation of the heat uniformly within the entire reaction mixture.
The reactor is also provided with a jacket which is connected with two sources of water, one being a hot source
0 0
which contains water at about 70 C and the other being a cold water source with water at about 30 C. This
water flow lines have their separate solenoid valves after which the meet through a T-joint and then the water
flows through the jacket.
The logic of the controller is set as such that at a time only one of the valve remains opened and the water
enters the jacket.
0 0
When the reactor temperature is below 58 C the hot water valve is opened and if it is above 58 C then the cold
0
water valve is opened. This ensures a steady maintenance of the reactor temperature around 58 C which is the
optimum temperature for our sulphonation reaction. Thus the conversion is maximized and maximum yield is
obtained.
A schematic diagram of the jacket along with water lines is shown below:
Fig 6.3
VI-3
Page 58
CHAPTER
RESULTS VII
AND
DISCUSSION
Page 59
Experiments are done both in batch and semi batch mode and the results are tallied which
clearly shows that in semi-batch mode conversion is obtained much faster than batch mode.
The data obtained are tabulated as follows :
7.1 BATCH MODE REACTION DATA
Sample
Time collected Hyamine Time Wt% of
Sl. no (min.) (gm) Density req. (ml) (min.) LABSA
1 1:51 0.43 1.078571 0 6 0
2 1:57 0.6 1.1 0.2 12 2.133333
3 2:04 0.72 1.073913 0.6 19 5.333333
4 2:11 0.5 1.134783 0.7 26 8.96
5 2:19 0.75 1.166667 0.9 34 7.68
6 2:32 0.74 1.035714 1.7 47 14.7027
7 2:42 0.396 1.075 1.2 57 19.39394
8 2:57 0.85 1.014375 2.1 72 15.81176
9 3:15 0.741 1.054375 1.9 90 16.41026
10 3:34 0.58 1.12381 1.5 109 16.55172
11 3:46 0.86 1.05625 2.4 121 17.86047
12 4:11 0.756 1.05 3.6 146 30.47619
13 4:26 0.6 1.055556 4 161 42.66667
14 4:45 0.6 1.107692 4.1 180 43.73333
Table 7.1
50
45
40
35
30
25
20 x-axis time in mins

15
y-axis %LABSA
10
5
0
0 50 100 150 200
Fig 7.1
VII-1
Page 60
7.2 SEMI BATCH MODE REACTION DATA
Time Temp. H2SO4 Sample Hyamine Wt% of

0
(min.) ( C) added(gm) collected(gm) req. (ml) LABSA
0 50 17.4 0
5 61 17.4 0.61 0.6 6.29508197
10 56 17.4 0.61 1.4 14.6885246
15 54 17.4 0.6 2.4 25.6
20 59 17.4 0.62 4 41.2903226
25 58 17.4
30 58 17.4 0.66 5.4 52.3636364
35 59 17.4
40 58 17.4
45 58 17.4 0.61 5.6 58.7540984
50 59 17.4
55 60 8.6
60 59 0 0.61 6.3 66.0983607
70 59 0
75 60 0 0.6 6.6 70.4
80 60 0
90 57 0 0.62 7.3 75.3548387
100 60 0
110 60 0
120 59 0 0.62 7.9 81.5483871
150 58 0 0.62 8.2 84.6451613
180 61 0 0.61 8.2 86.0327869
Table 7.2
VII-2
Page 61
100
90
80
70
60
50
x-axis time in mins
40
30 y-axis %LABSA
20
10
0 20 40 60 80 100 120 140 160 180 200
Fig 7.2
After 180 mins of reaction, we can see that in batch mode weight percent of LABSA
obtained is only about 43.73% whereas in semi-batch mode it is about 86.03%.
VII-3
Page 62
The above figure clearly depicts the difference between the two modes of reaction
where in the right hand side we see much better conversion with a thin slit of unreacted LAB at
the top, and a thicker whitish band that represents the LABSA phase. The lower dark phase
represents spent sulphuric acid.
In this regard, it is to be added that the best way is to run the reaction in continuous
mode with SO3 as sulphonating agent but that cannot be done due to emission norms since
emission of SOx compounds will exceed the allowable limits.
So it may be said that the optimized way is to carry on the reaction in semi batch mode
with proper temperature control for maximum yield.
VII-4
Page 63
CHAPTER VIII
OPTIMIZATION OF VITAL
PARAMETERS
Page 64
8.1 Optimized H2SO4/LAB ratio for final yield:
An important parameter for LABSA production is the ratio of moles of H2SO4 used to that of
LAB. As this ratio increases, the final yield i.e. (w/w) % of LABSA increases and formation of
undesired byproducts, sulfones can be reduced by using an optimum value of the ratio.
Simulation for this reaction system using various values of the ratio produced different yields,
among which the maximum yield is found to be 92.4 (w/w) % LABSA for acid to LAB mole
ratio of 1.08.
The results are illustrated in Fig 8.1 below.
VIII-1
Page 65
8.2 Optimized Batch Time:
During simulation another parameter cycle-time, which is the sum of on-off time, has also optimized
since, it has certain effects on total batch-time. Based on a cycle time of 17 sec consisting of on-time 7 sec
and off-time 10 sec , the total batch time has found to be a value of 160 min, at the acid to mole ratio of
1.08 and for the maximum yield of 92.4 (w/w) % of LABSA. The results are discussed in the Fig 8.2.
Fig 8.2: Total Batch time vs Cycle time Fig 8.3: Wt% of LABSA vs Reaction Temperature
8.3 Optimization of Reaction Temperature:
Varying the reaction temperature i.e. reaction rate constant in the simulation program, several
value of final yield has found. From which, it has concluded that as temperature rises the final yield also
rises. At a value of 650C it becomes 93.1 (w/w) % of LABSA. But from the experiments in the laboratory
it has been found that the product quality (in terms of color) deteriorates at the 650C. So the temperature
should be kept below 600C, at which the final yield has been found to a value of 92.4 (w/w) % of LABSA
for the acid to LAB mole ratio of 1.08. The different results are shown in the Fig 8.3.
VIII-2
Page 66
CHAPTER IX
CONCLUSION
Page 67
CONCLUSION
The present study has vividly demonstrated the advantages of optimizing the LAB
sulphonation process by modifying the current procedures followed in the industry. The batch
process followed in industry is time consuming in one hand and also inefficient in terms of
controlling the extreme non linearity of the system because with minute changes in the mole
ratio of reactants, reactor temperature, rpm of the agitator there is marked effect on the reaction
which ultimately hampers yield of LABSA.
We have changed the mode of reaction to semi batch nature and used pulsed feeding technique
while feeding the acid through the help of solenoid valve thus decreased the generation of heat.
Moreover, in the industry direct cooling of the reaction mixture is done by quenching with
water. This is very detrimental since dilution of the spent acid causes further rise in the
temperature. Again, the volume is increased manifold times, thus decreasing the concentration
of LABSA, so need for separation of the excess water comes into consideration.
In our project, indirect cooling through jacket is provided, which not only restrains excessive
heating of the reactor but also has the capability of switching from cool to hot mode if the
temperature drops down. This unique feature enhances the control over the reactor temperature
and thus enables us to carry out the reaction close to the optimum temperature which
maximizes conversion.
Thus, on a nutshell, this project will be a practical and profitable way to be followed by the
industry to handle this sulphonation reaction and carry on the production process smoothly.
IX-1
Page 68
NOMENCLATURES
ANOVA : Analysis of Variance
CCD : Central Composite Design
CMC : Carboxy Methyl Cellulose
CV : Co-efficient of Variance
DDB : Dodecylbenzene
LAB : Linear Alkyl Benzene
LAS : Linear Alkylsulfonate
LABSA : Linear Alkyl Benzene Sulfonic Acid
LDR : Light Detecting Resistance
RSM : Response Surface Methodology
d, Da : Stirrer Diameter [m]
D : Tank Diameter [m]
E : Activation Energy [kJ/mol]
H : Tank Height [m]
Kow : Solubility of LABSA in Water
kt : Rate Constant for Second Order Reaction[(mol/lit)-1 (min)-1]
M : Concentration Ratio of LAB to H2SO4
NRe : Reynolds Number
NP : Power Number
n : rpm of Stirrer
P : Power required for mixing [Watt]
Page 69
R : Universal Gas Constant [8.314 J/mol-K]
R1 : Response Variable in RSM domain
rps, rpm : Revolution per second , minute respectively
t : Temperature of the reaction mixture at any time [0C]
tm : Mixing Time [sec]
: Density of the solution [gm/cc]
: Absolute Viscosity of the solution [cP]
Page 70
REFERENCES/BIBLIOGRAPHY
MORENO, A., BRAVO, J., and BERNA, J. L., Influence of Unsulphonated material and its sulphone
content on the physical proiperties of Linear Alkyl Sulphonates, JOURNAL OF AMERICAN OIL
CHEMICAL SOCIETY (1988).
SILVA, E.M., ROGEZ, H., LARONDELLE, Y., Optimization of extraction of phenolics from Inga
edulis leaves using response surface methodology SEPERATION PURIFICATION TECHNOLOGY,
VOL. 55, NO 3, (2007) 381387.
RUSHTON, J.H. and OLDSHUE, J.Y., Ibid., VOL.49, (1953),178.
QING-HUA, H., YIN, L.J., SHU-JUN, L., YANG, B.N., MA, J.W., Optimization of process parameters
for microwave vacuum drying of apple slices using Response surface method, DRYING TECHNOLOGY,
VOL. 28, NO. 4, (2010), 523-532.
QUANHONG, L., CAILI, F., Application of response surface methodology for extraction optimization of
germinant pumpkin seeds protein , FOOD CHEMISTRY,VOL. 92,NO.4 (2005) 701706.

ROBERT, D.W. and MARLEY, J.O., A molecular orbital study of the mechanism of Alkyl Benzene
Sulphonation, PROCEEDINGS OF XXVII JORNADAS DEL COMITE ESPANOL DE LA
DETERGENCIA(CED),BARCELONA, SPAIN (1997).
ROBERTS, D.W., Optimization of the Linear Alkyl benzene Sulfonation Process, UNILEVER
RESEARCH AND DEVELOPMENT, WIRRAL, UK) ORGANIC PROCESS RESEARCH
&DEVELOPMENT 2003, 7(2), 172-184.
RUSHTON, J.H., CHEMICAL ENGINEERING PROGRESS,VOL.48,(1952),33,95.
RUSHTON, J.H., COSTICH, E.W. and EVERETT, J.H., Ibid.,VOL.46,(1950),395,472.
Page 71
VAN DE VUSSE, J.G., Mixing by agitation of miscible liquids Part I, CHEMICAL ENGINEERING
SCIENCE, VOL.4, (1955), 178.
WANI, A.A., SOGI, D.S., GROVER, L., SAXENA, D.C., Effect of Temperature, Alkali
Concentration, Mixing Time and Meal/Solvent Ratio on the Extraction of Watermelon Seed Proteinsa
Response Surface Approach, BIOSYSTEMS ENGINEERING ,VOL.94, NO.1, (2006) 67 73.
ZHOU, P., REGENSTEIN, J.M.., Optimization of extraction conditions for Pollock skin gelation,
JOURNAL OF FOOD SCIENCE, VOL. 69, NO. 5, (2004), C393C398.
BOOKS
DANIEL, W.W., (1991). BIOSTATISTICS: A FOUNDATION FOR ANALYSIS IN THE HEALTH SCIENCES
(5TH ED.). NEW YORK: WILEY.
GILBERT, E.E., (1965).SULPHONATION AND RELATED REACTIONS. INTERSCIENCE
PUBLISHERS,NEWYORK .
GROOT, W.H.D., (1991). SULPHONATION TECHNOLOGY IN THE DETERGENT INDUSTRY.
KLUWER ACADEMIC PUBLISHERS, NORWELL, MA.
LITTLE, T.M. & HILLS, F. J., (1978). AGRICULTURAL EXPERIMENTATION DESIGN AND ANALYSIS
.NEW YORK: JOHN WILEY.
MENDENHALL, W., (1975). INTRODUCTION TO PROBABILITY AND STATISTICS (4TH ED.). NORTH
SETTUATE, MA: DUXBURY PRESS.
MONTGOMERY, D. C., (2001). DESIGN AND ANALYSIS OF EXPERIMENTS (5TH ED.). NEW YORK:
WILEY. PP. 455492.
STERBACEK, Z. & TAUSK, P. (1965). MIXING IN THE CHEMICAL INDUSTRY ( 1ST ED.). OXFORD,
NEW YORK: PERGAMON PRESS. P.111.

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FEEDING STRATEGY OPTIMIZATION

CLASS ROLL NO: 001110302004

REGISTRATION NO: 116773 of 2011-12

EXAMINATION ROLL NO: M4CHE13-04

UNDER THE GUIDANCE OF

DEPARTMENT OF CHEMICAL ENGINEERING

Declaration of Originality and Compliance of Academic Ethics

work by the undersigned candidate, as part of his MASTER OF CHEMICAL

All information in this document have been obtained and presented in

accordance with academic rules and ethical conduct.

NAME : DEBASISH MUKERJEE

EXAMINATION ROLL NO : M4CHE13-04

THESIS TITLE : FEEDING STRATEGY OPTIMIZATION OF

SIGNATURE WITH DATE :

This is to certify that the thesis entitled FEEDING STRATEGY OPTIMIZATION OF

CHAPTER I INTRODUCTION I-1 TO I-6

1.1 INTRODUCTION I-1

1.2 REACTION WITH SO3 I-2

1.3 SULFONATION PROCESS I-3

1.4 ROUTE OF THE REACTION I-4

CHAPTER II PROCESS IDENTIFICATION II-1 TO II-6

2.1 CHEMICAL IDENTITY II-1

2.4 REACTIVITY DATA II-2

2.5 HEALTH HAZARD DATA II-2

2.6 PREVENTIVE MEASURES II-3

2.7 ADDITIONAL INFORATIONS AND REFERENCES II-3

2.8 HAZARDS IDENTIFICATION II-4

2.9 PROPERTIES OF LAB, H2SO4, LABSA II-4

2.10 HEAT BALANCE FOR SULFONATION PLANT II-5

CHAPTER III GENERAL SCOPE, PROCESS

3.1 OBJECTIVE OF THE PROJECT III-1

3.2 METHODOLOGY III-1

3.3 SCOPE OF APPLICATION III-2

3.4 ECO- FRIENDLY CHARACTERISTICS III-3

3.5 PRESENT SCENARIO III-3

CHAPTER IV REVIEW OF LITERATURE IV-1 TO IV-8

4.1 LITERATURE RELATED TO SULFONATION IV-6

CHAPTER V MATERIALS USED AND EQUIPMENT V-1 TO V-13

CHAPTER VI CONTROL MECHANISM VI-1 TO VI-3

6.1 CONTROL OVER THE GENERATION OF HEAT VI-1

6.2 CONTROL OF HEAT ALREADY GENERATED VI-3

CHAPTER VII RESULTS AND DISCUSSION VII-1 TO VII-2

7.1 BATCH MODE REACTION DATA VII-1

7.2 SEMI BATCH MODE REACTION DATA VII-2

CHAPTER VIII OPTIMIZATION OF VITAL PARAMETERS VIII-1 TO VIII-2

8.1 OPTIMIZED H2SO4/LAB RATIO FOR FINAL YIELD VIII-1

8.2 OPTIMIZED BATCH TIME VIII-2

8.3 OPTIMIZATION OF REACTION TEMPERATURE VIII-2

CHAPTER IX CONCLUSION IX-1

The Linearalkylbenzene (LAB) Sulfonic-acids coalition is sponsoring three Linearalkylbenzene

LAS are included to provide supporting information for the category.

any significant areas of concern for the LAB sulfonic acids.

quantitative determination was only established by liquid chromatography-mass spectroscopy in 1996

and final simulation of the sulfonation reaction in a reactor.

Table 1.1: TYPICAL ALKYL CHAIN COMPOSITION

1.2 REACTION WITH SO3

should be reduced to minimize the production of production of sulfones and anhydrides.

formed according to the reaction.

1.3 SULFONATION PROCESS

stocks and producing excellent quality products from all of them.

making a broad range of very high quality products.