1

Contents
List of figures ........................................................................................................................ 2
List of tables ......................................................................................................................... 2
CHAPTER 1 ......................................................................................................................... 3
PROCESS BACKGROUND ........................................................................................................... 3
1.1

Introduction of Sodium Lauryl Ether Sulfate(SLES) ....................................................... 3

1.2

Physical and Chemical Properties of Sodium Lauryl Ether Sulfate(SLES) ................ 4

1.3

History of production ........................................................................................................... 5

1.4

Lauryl alcohol as Raw Material .......................................................................................... 6

1.4.1 Advantages of lauryl alcohol ............................................................................................ 7

1.5

Sodium Lauryl Ether Sulfate (SLES) feedstock .............................................................. 7

1.5.1

Lauryl alcohol (Dodecanol)......................................................................................... 7

1.5.2

Sulfur.............................................................................................................................. 8

1.5.3

Air ................................................................................................................................... 9

1.5.4

Vanadium pentoxide.................................................................................................. 10

1.6

Application of Sodium Lauryl Sulfate (SLES) ................................................................ 11

1.7

Process comparison .......................................................................................................... 11

1.7.1.

Sulfation process ....................................................................................................... 12

1.7.2

Neutralization process............................................................................................... 18

1.7.3

Ethoxylation process ................................................................................................. 19

1.8

Selected method ................................................................................................................ 21

1.8.1

Process Details .......................................................................................................... 23

REFERENCES ............................................................................................................................... 26
APPENDIX ...................................................................................................................................... 28

List of figures
Figure 1.1: Chemical structure of alcohol ethoxysulfate...3
Figure 1.2: Molecular structure Sodium Lauryl Ether Sulfate (SLES).4
Figure 1.3: Molecular structure lauryl alcohol ....8
Figure 1.4: Liquid Sulfur......8
Figure 1.5: Air composition....9
Figure 1.6: Solid vanadium pentoxide ...10
Figure 1.7: Chemical reaction of production sulfur trioxide10
Figure 1.8: Process Flow Diagram of Sodium Lauryl Ether Sulfate (SLES)11
Figure 1.9: Process Flow Diagram of the selected process....23

List of tables
Table 1.1: The properties of SLES ...4
Table 1.2 : Properties of lauryl alcohol.8
Table 1.3: Properties of sulfur9
Table 1.4 Comparison between sulfation processes15
Table 1.5 Comparison between ethoxylation processes.20
Table 1.6: Reactions in the production of SLES24
Table 1.7: Kinetic data for reaction in Sulfation Process.25

CHAPTER 1

PROCESS BACKGROUND

1.1

Introduction of Sodium Lauryl Ether Sulfate(SLES)

Figure 1.1 : Chemical structure of alcohol ethoxysulfate

Alcohol ethoxysulfate is widely known as a surfactant. The definition of surfactant, or a

surface active agent is a molecule that consist of both hydrophilic and also hydrophobic
parts which will attract the polar and nonpolar surfaces. The hydrophilic part originates from
ethoxylate chain while the hydrophobic part is originated from alcohol chain. This is what
makes surfactant such a good cleaning agent as it is soluble in polar liquids such as water
and also non polar liquid such as oil.

4
As seen in the above figure, alcohol ethoxysulfate consists of the long chain of
carbon and hydrogen which contributes to high boiling and melting point. This is because
long chain of chemical structure means stability and strength of the compound, thus
increasing the temperature to break the bond. The solubility of AES is mainly affected by the
alcohol chain. Aside from that, the addition of ethylene oxide in this compound also
positively influences the solubility of AES, by means the solubility in water increases as the
ethylene oxide is put together.

Sodium lauryl ether sulphate, CH3(CH2)11(OCH2CH2)nOSO3Na, also known as SLES

is a type of surfactant that is widely used in detergent industry. As seen in Figure 1.1, it is
composed by carbon, hydrogen, sodium, sulphur and oxygen compounds. SLES originates
from fatty alcohols such as lauryl alcohol, which is gained from fatty acids usually obtained
from palm oil, coconut oil and petroleum.

1.2

Physical and Chemical Properties of Sodium Lauryl Ether Sulfate(SLES)

Figure 1.2 Molecular structure Sodium Lauryl Ether Sulfate(SLES)

Sodium lauryl sulphate, which is an alcohol ethoxysulfate, appears to be in solid state at

room temperature. Usually it is in fine, white powder. It is found that melting point of SLES is
10-15C while the boiling point is 100C.

Table 1.1: The properties of SLES

Properties

Description

Physical state and appearance

Solid state at room temperature

Odor

Odourless

Molecular Formula

C12H250(C2H4O)1SO3Na

Molecular Weight

332.05 g/mol

Density

1.1 g/cm3

Colour

White

1.3

Boiling point

100C

Melting point

10-15C

Flash point

94C

Solubility in water

Soluble in water at 452 mg/L

Specific gravity

1.05

Stability

Stable

History of production

The origin of sodium lauryl sulphate is from fatty alcohols. These fatty alcohols can be
obtained from fatty acids, which have several sources such as coconut oil, palm oil and
even petroleum. The easiest way to produce fatty alcohol is by hydrogenation process,
introduced by Paul Sabatier in 1912, whom is considered as the father of hydrogenation
process.

Fatty alcohol, usually lauryl alcohol is then proceeds to the sulfation process. Up to
1960, a lot of researches have been indulging and involving with sulfation process. This
process would require a reactor as chemical reaction takes place in order to produce lauryl
alcohol sulphate. For sulfation process to occur successfully, lauryl alcohol reacts with
sulphur trioxide and air inside the reactor. Sulphuric acid is also added with a small amount,
just to assure the viscosity of the intermediate product is low.

As the intermediate product, lauryl alcohol sulphate is high in acid level,

neutralization process is needed to increase the pH value so that the usage and application
of this product will be safe to the consumers. Commonly in this process, sodium hydroxide
or sodium carbonate is widely used. Sodium lauryl sulphate (SLS) is discharged from this
process.

Lastly, SLS will enter a reactor for ethoxylation process. This process will convert
SLS into sodium lauryl sulphate (SLES). It requires ethylene oxide as the reactant and
potassium hydroxide as the catalyst. The catalyst can be used in a multiple times and can
be regenerated on-site.

6
1.4

Lauryl alcohol as Raw Material

Fatty alcohols play a major role in the Oleochemicals industry. They are components also of
cosmetic, foods and as industrial solvent. Fatty alcohol derived from natural fats and oils.
Some commercially imported fatty alcohols are lauryl, stearyl and oleyl alcohols. Fatty
alcohols or long-chain alcohols are usually high-molecular-weight, straight-chain primary
alcohols, but can also range from as few as 4-6 carbons to as many as 22-26. The lower
chainlengths (C2-C10) are liquid at room temperature, whereas above C10 they vary from
low melting colourless crystalline materials to white waxy solids (C16-C18), melting around
55C.

They are colourless oily liquids (for smaller carbon numbers) or waxy solids,
although impure samples may appear yellow. Fatty alcohols usually have an even number
of carbon atoms and a single alcohol group (-OH) attached to the terminal carbon. Some are
unsaturated and some are branched. They are widely used in industry. As with fatty acids,
they are often referred to generically by the number of carbon atoms in the molecule, such
as "a C12 alcohol", that is an alcohol having 12 carbons, for example dodecanol or lauryl
alcohol.

Lauryl alcohol plays a major role in the production of detergent and surfactant. Due
to their amphipathic nature, fatty alcohols behave as surfactant. They find use as emulsifier,
emollients and thickeners in cosmetics and food industry. About 50% of fatty alcohols used
commercially are of natural origin, the reminder being synthetic.

A C12-C18 alcohol is known as detergent range alcohols. Detergent uses in one

form or other consume the largest proportion of alcohol produced. This usage depends on
the ability of the alcohol to add fat-loving or lipophilic character to the detergent molecule.
Alcohols are successful here and also provide, via the hydroxyl group, a reactive site which
can add water-loving (hydrophilic) character of varying intensity depending on which
chemical groupings get reacted into the molecule. This hydrophilic-lipophilic balance (or
HLB) is key in identifying which detergents are good for removing fatty soiling and which
remove non-fatty material.

7
The HLB is generally modified through sulphation (reaction with sulphur trioxide in
some form) to produce an alcohol sulphate, or through ethoxylation (reaction with ethylene
oxide) to produce ethoxylates which can then be sulphated and used as is. These sulphates
and ethoxylates are the active cleansing ingredients in laundry detergents, shampoos and
shower gels.

1.4.1 Advantages of lauryl alcohol

The use of lauryl alcohol as starting materials for many others raw materials is rapidly
gaining ground because of the following advantages:
1. Large scale feedstock.The sources of lauryl alcohol have largely been various
vegetable oils. Plant sources are more variable compare to animal fats. Example of
plant sources of lauryl alcohols are obtained from coconut iol or palm oil. The
alcohols are isolated from the triglycerides (fatty acid triesters), which form the bulk
of the oil, by transesterification to give methyl esters which in turn are hydrogenated
to the alcohols
2. A low level of toxicity from inhalation, oral or dermal exposure. Lauryl alcohols are
not very volatile and the acute lethal concentration is greater than the saturated
vapor pressure. Lauryl alcohols produce fewer health effects compare to others
materials.
3. Lauryl alcohol are biodegradable. The time taken of biodegradable process is within
10 days completely. At waste-water treatment plants have shown that 99% of lauryl
alcohols are removed. Lauryl alcohol while in water partition into sediment and stay
in the air upon release. Lauryl alcohol will respond independently upon
environmental release.

1.5

Sodium Lauryl Ether Sulfate (SLES) feedstock

The sodium lauryl ether sulfate (SLES) feed stock are lauryl alcohol, sulfur and air.
1.5.1

Lauryl alcohol (Dodecanol)

Dodecanol is an organic compound with the chemical formula CH3(CH2)10CH2OH or

C12H26O. It is tasteless, colorless solid with a floral smell. It is classified as a fatty alcohol.

Figure 1.3: Molecular structure lauryl alcohol

The IUPAC name of dodecanol is dodecan-1-ol. The others names are dodecanol, 1dodecanol, dodecyl alcohol and lauryl alcohol. Lauryl alcohol is soluble in ethanol and
diethyl ether. Lauryl alcohol is used to make surfactant, lubricating oils, pharmaceuticals, in
formation of monolithic polymers and as a flavor enhancing food additive. In cosmetics,
lauryl alcohol is used as an emollient. In 1993, the European demand of lauryl alcohol
around 60 thousand tons per year. It can be obtained from palm kernel or coconut oil fatty
acids and methyl esters by hydrogenation.

Table 1.2: Properties of lauryl alcohol

1.5.2

Properties

Description

Molar mass

186.34 kmol/kg

Density

0.8309 g cm -3

Melting point

24 C

Boiling point

259 C

Sulfur

Figure 1.4: Liquid Sulfur

9
Sulfur or sulphur is a chemical element with symbol S and atomic number 16. It is abundant,
multivalent non-metal. Elemental sulfur is a bright yellow crystalline solid when at room
temperature. Chemically, sulfur can react as either an oxidant or a reducing agent. It
oxidizes most metals and several nonmetals, including carbon, which leads to its negative
charge in most organosulfur compounds, but it reduces several strong oxidants such as
oxygen and fluorine. Sulfur occurs naturally as the pure element and as sulfide and sulfate
minerals. Today, almost all elemental sulfur is produced as a byproduct of removing sulfurcontaining contaminants from natural gas and petroleum. Many surfactants and detergents,
e.g sodium lauryl sulfate, are produced are sulfate derivative.

Table 1.3: Properties of sulfur

1.5.3

Properties

Description

Molar mass

186.34 mol/g

Density

2.07 g cm -3

Melting point

115.21 C

Boiling point

444.6 C

Air

Figure 1.5: Air composition

The common name given to the atmospheric gases used in breathing and photosynthesis is
air. By volume, dry air contains 78% nitrogen, 20.95% oxygen, 0.97% argon, 0.03% carbon
dioxide and small amounts of other gases. Air also contains a variable amount of water
vapor, on average around 1% at sea level, and 0.4% over the entire atmosphere. In most

10
industrial application and in fires, air is the source of oxygen (O2). Oxygen in air act as
oxidant in burning/combustion process.
1.5.4

Vanadium pentoxide

Figure 1.6: Solid vanadium pentoxide

Vanadium(V) oxide is inorganic compound with the molecular formula V2O5. IUPAC name
is Divanadium pentaoxide, other names are vanadium pentoxide, vanadic anhydride and
divanadium pentoxide. Commonly known as vanadium pentoxide, it is a brown/yellow yellow
solid. In aqueous solution, its formed a deep orange color with precipitated. Because of its
high oxidation state, are both an amphoteric oxide and an oxidizing agent. In industrial, it is
important of vanadium, being principal precursor and widely used industrial catalyst.

Figure 1.7: Chemical reaction of production sulfur trioxide

Use vanadium pentoxide in manufacture of sulphuric acid, an important industrial chemical

with an annual worldwide production. Vanadium pentoxide serves the crucial purpose of
catalysing the mildly exothermic oxidation of sulfur dioxide to sulfur trioxide by air in the
contact process : Vanadium pentoxide is the most effective catalyst for produced sulfur
trioxide with cheap substances for industry today.

11
1.6

Application of Sodium Lauryl Sulfate (SLES)

Widely used in liquid detergent such as dishwashing detergent, shampoo, bubble

bath liquid, hand washing etc.

In washing powder and detergent for heavy dirty, using it to partially replace linear
alkylbenzene sulphonic acid (LABSA).

In textile, printing and dyeing industry, petroleum and leather industry, it can be used
as lubricant, dyeing agent, cleanser, foaming agent and degreasing agent.

Good cleaning, emulsifying, wetting, densifying and foaming performance, with good
solvency, wide compatibility, strong resistance to hard water, high biodegradation,
and low irritation to skin and eye.

1.7

Process comparison

Figure 1.8: Process Flow Diagram of Sodium Lauryl Ether Sulfate (SLES)

12
Process selection was made by comparing the three processes with the objective to
minimize the capital cost, maximize profit and environmental friendly. Factor such as
operating temperature, operating pressure, selectivity, catalyst consumption in the reactor
are influenced the process selection. In addition, environment consideration and safety also
influenced the selection of the process. As more waste produced requires more capital cost
to be invested in order to minimize the waste. Apart from that, the process that has many
critical conditions will contribute to highly hazard. The process that have highly hazard need
a lot safety measure and give high capital cost.
1.7.1. Sulfation process
Sulfation are major industrial chemical processes used to make a diverse range of products,
including dyes and color intensifiers, pigments, medicinals, pesticides and organic
intermediates. Additionally, almost 500,000 metric tons per year of lignin sulfonates are
produced as a by-product from paper pulping. Petroleum sulfonates are widely used as
detergent additives in lubricating oils. However, the majority of the 1.6 million metric tons of
sulfonates and sulfates produced annually in the United States are used as surfactants in
laundry and consumer products applications. This chapter focuses only on commercial
techniques for production of detergent range sulfonates and sulfates.

1.7.1.1 Sulfamic acid

Sulfamic acid is is one of the most frequent reactants used in sulfation process, especially in
sulfation of alkyl phenol ethoxylates. This price of equipment for this compound is low and
the pressure is applied at 100 mmHg, but the temperature used is rather high which is in
between range of 90C and 150C. Furthermore, another disadvantage occurred as
sulfamic acid cannot sulfonate aromatic ring, thus leaving a good amount of the alcohol
remains the same, without undergoing sulfation.
1.7.1.2 Chlorosulfonic acid
In the production of alcohol sulfates and alcohol ether sulfates, cholorosulfonic acid is often
chosen. This is because this substance holds an advantage which is it is capable of
undergoing sulfation of lauryl alcohol without damaging the product by degradation or
decolourisation. However, the side effect of this process is that it produces hydrochloric
acid, thus requires scrubbing or recovery process afterward. Aside from that, due to the by-

13
product, this process is considered as hazardous and not recommended by the
environmental activists.
1.7.1.3 Air/SO3
Possible sources of SO3 gas used for an air/SO3 sulfation system are:
Sulfuric acid plant converter gas
Converter gas from a sulfuric acid plant contains 1012% SO3 and appears to be a potential
SO3 source for sulfation. There are several problems with using a sulfuric acid plant as an
SO3 source for sulfation. Nevertheless, such an arrangement has been commercially
installed and at first glance appears to be an attractive, low cost method of supplying SO3
gas to a sulfation plant. Physical location is a limiting factor; as the sulfation plant must be
installed as closely as possible to the sulfuric acid plant converter. In addition, the sulfation
plant can run only when the sulfuric acid plant is running.
Liquid SO3
Some of the first air/SO3 sulfation plants installed were based on use of liquid SO3. These
plants require an air supply system identical to the system described below for a sulfur
burning plant except that it also requires an external heat source for air dryer regeneration.
In addition, a liquid SO3 plant requires an SO3 storage system. This storage system is
usually a large 20,000 to 80,000 kg storage tank located in a heated room and maintained at
a temperature of about 4043C. Heating the SO3 storage room can be a significant cost in
colder climates. In case of SO3 leaks, the room must be sealed and should have provision
for scrubbing any SO3 that escapes into the room's atmosphere.
Sulfur burning in equipment specifically designed to produce SO3 gas for sulfation
With sulfur burning air/SO3 sulfation processes, the only SO3 on site is the small quantity of
dilute gaseous material in the process piping between the converter (SO2 to SO3) and the
sulfation reactor. Even in the world's largest sulfation plant (20,000 kg/hr active
production),this amounts to only about 100 kg of dilute SO3 gas. The sulfur burning process
is much safer than transporting, storing and handling tank truck (18,000 kg) or rail car
(72,000 kg) quantities of oleum or liquid SO3

14
The basic plant package for a sulfur burning, air/SO3 sulfonation installation includes a
sulfur supply system, air supply system, SO3 gas plant system, SO3 absorber
system,sulfonator, neutralizer, effluent gas clean-up system, control system and motor
control center. Additional equipment as required to manufacture specialty products, such as
a hydrolyzer for alpha olefin sulfonate production, re-esterfication and bleaching equipment
for methyl ester sulfonate production, dioxane strippers for production of ethoxy alcohol
sulfates containing ultra low dioxane levels (less than 10 ppm), and dryers for producing
concentrated,pure detergent active. Capacities for commercial sulfur burning air/SO3
sulfonation units range from 250 to 20,000 kg/hr of 100% detergent active. Typically, an
air/SO3 sulfonation plant is designed to sulfonate with approximately 47% (volume) SO3.
However, if you plan to use ethoxylated alcohol as a major feedstock, the SO3 gas
concentration may be as low as 2.75% SO3 in air to the sulfation systems.

15
Table 1.4: Comparison between sulfation processes
Process

Mechanism

Sulfamic Acid Sulfation

Chlorosulfonic acid sulfation

-Sulfamic acid is used to sulfate

-chlorosulfuric acid used to produce - SO3 gas is diluted with very dry air

alcohols and ethoxylated

alcohol sulfates, alcohol ether

and reacted directly with the organic

alcohols to from an ammonium

sulfates and etc.

feedstock

neutralized salt.

Air/SO3 sulfation

-typically air/SO3 sulfated alcohols

and alcohol ether sulfates.

Raw material

Cost Raw Material

Product

By-Product

Advantages

(4)

(4)

(5)

Sulfamic acid

Chlorosulfuric acid

Sulfur

(2)

(1)

(4)

US$0.51 per pound

US$0.255 per pound

US$0.02 per pound

(1)

(3)

(5)

Alcohol sulphates

Alcohol sulphates

Alcohol sulphates

(5)

(5)

(5)

HCl

(5)

(2)

(3)

-major use of sulfation of akyl

- sulfated lauryl alcohol without

- only SO3 on site is the small

phenol ethoxylates.

degradation or discolouration

quantity of dilute gaseous

(3)

(3)

material in the process piping

between the converter (SO2 to SO3)
and the sulfation reactor.

16
-large scale continuous process
best suited to 24 hours per day,
seven days per week manufacture
of tons per hour of
product.
(3)
Disadvantages

-Sulfamic acid is that it

-reaction moves to completion,

selectively sulfates alcohol

hydrochloric acid (HCL) is released

(3)

group and will not sulfonate

-need to scrubbed or recovered.

aromatic rings.

-corrosion & hazardous because

(2)

HCL is the by-product

(1)

Type of process

-batch process

-batch process

-a continuous process

(2)

(2)

(4)

Process equipment

Low

Low

High

cost

(3)

(3)

(2)

Temperature

90 to 150 C

-90C

20-80C

(2)

(2)

-50C/60C
(4)

Catalyst

Pressure

Amide

Vanadium pentoxide

(3)

(1)

(3)

100 mm Hg / 0.13 atm

1 atm

15 psig / 1.020 atm

(3)

(5)

(4)

17
Patented Process

Total

NO

NO

YES

(2)

(2)

(4)

37

34

49

18
1.7.2

Neutralization process

In a continuous neutralizer system, neutralizer combines sulfonic acid or organo-sulfuric acid

with a neutralizing agent, additives, and diluents (water), in dominant bath neutralization.
The result is a solution of neutral active matter (slurry or paste) of the desired composition
and pH. Caustic soda, usually NaOH, is the most common neutralizing agent. However,
caustic potash, aqueous ammonia, triethanolamine, and other agents are compatible with
the neutralizer.

A process for neutralizing an organic sulfuric or sulfonic detergent acid, e.g.,lauryl

sulfuric acid or mixture of such acids, in liquid state, with a liquid solution or slurry of
neutralizing agent of a low moisture content is conducted in a wiped film neutralizing reactor
wherein a film of the organic acid and neutralizing agent is formed on an internal wall of the
reactor, which wall (with the film) is continuously wiped during the neutralization reaction by
a wall scraper or a plurality of scrapers which also agitate the reactants, whereby there is
produced a pumpable aqueous slurry, having a high concentration of the detergent salt
solids which is above a gel region which prevents the concentration of such detergents ade
by other processes that produce lower detergent concentrations. During the reaction, which
is usually preferably conducted under atmospheric, the heat generated is removed, usually
by evaporation of water, so as to maintain a desirable temperature for the neutralization.
Also within the invention are processes wherein the wiped film neutralizing reactor is
employed in conjunction with a film reactor for sulfating or sulfonating organic material, such
as lauryl alcohol, to the corresponding detergent acid and soon after production there of
neutralizing such acid in the wiped film neutralizing reactor as well as the apparatus for
practicing these processes.

19
1.7.3

Ethoxylation process

Ethoxylates are generally obtained by additions of ethylene oxide (EO) to compounds

containing dissociated protons. Substrates used for ethoxylation are primarily linear and
branched C12-C18 alcohols, alkyl phenols, nonyl (propylene trimer) or decyl (propylene
tetramer) groups, fatty acids and fatty acid derivatives. The addition of EO to a substrate
containing acidic hydrogen is catalyzed by bases or Lewis acids .Amphoteric catalysts, as
well as heterogeneous catalysts are also used. The degree of ethoxylation ( the moles of
EO added per mole of substrate ) varies over wide ranges, in general between 3 and 40,
and is chosen according to the intended use.

1.7.3.1 Semi-batch
Worldwide, the majority of ethoxylates used in detergents are produced via semi-batch
processes utilizing base catalysis, typically potassium hydroxide (KOH). As such ethoxylates
are commodity materials, the production economics and capability to manufacture the
precursors are important determinants of profitability. Currently, only a small fraction of such
surfactants are produced with specialized catalysts which give a narrow molecular weight
distribution. Although the narrow distribution products from such processes can give higher
performance in most applications, the cost driven focus of the detergent industry dictates the
use of the KOH-catalyzed, wide distribution products because the benefits of enhanced
performance are not sufficient to offset the increased costs.

The semi-batch process is the industry standard and although it is has been
optimized and refined, there remain disadvantages to the use of this process. The semibatch process operates with a headspace of ethylene oxide and an inerting gas and there
are several nonproductive steps in the reactor sequence. Because pure ethylene oxide can
present a hazard, the headspace must be inerted with nitrogen or low oxygen content gas
and at the end of the cycle this inerting gas which may contain traces of ethylene oxide must
be wasted. In the sequence of nonproductive steps: the alcohol is charged followed by
catalyst and then the base is converted to the potassium or sodium alkoxide by stripping to
remove water after the mixture is heated to process temperature. After oxide addition and
digestion, the product is pumped from the reactor.

20
1.7.3.2 Continuous
The present invention provides continuous processes for the production of an ethoxylate
from a C1 - C26 non-phenolic alcohol in the presence of a double metal cyanide ("DMC")
catalyst. The inventive multi-stage continuous process produces an ethoxylate product with
an essentially equivalent molecular weight distribution as compared to the same ethoxylate
made by basic catalysis. The inventive single-stage continuous process produces ethoxylate
products having only a slightly broader molecular weight distribution than the multi-stage
process. The products made by the inventive multi-stage continuous process may offer
advantages where the ethoxylate product is used in or as a surfactant. Because of its
unique features, the DMC catalyst provides a poor distribution of ethylene oxide when the
equivalent weight of the base polyol is greater than about 800. The production of ethylene
oxide ("EO") capped polyols suitable for use in polyurethanes requires either a two-stage
system of DMC and potassium hydroxide or potassium hydroxide alone as the catalyst.
Thus, although DMC catalysts are very effective for the production of ethoxylates when the
starter equivalent weight is less than about 800, these capped low molecular weight polyols
are not widely used for the production of polyurethanes.

Table 1.5 Comparison between ethoxylation processes

Type of Process

Semi Batch

Continuous

Type of Catalyst

KOH (Potassium hydroxide)

Double Metal Cyanide (DMC)

(4)

(2)

120 - 150C

130 - 180C

(4)

(3)

5 bars

2 3 bars

(3)

(4)

1. Industry standard and has

1. Shorter residence time

Temperature

Pressure

Advantages

been optimized and refined

2. Better yield of product

many times.

3. Same or narrower molecular

2. Cheap & easy to acquire

catalyst
3. Low manufacturing cost
4. Catalyst are easily
recoverable from the

weight distribution
(3)

21
product.
(4)
Disadvantages

1. Operates with a headspace

1. Higher cost of catalyst

of ethylene oxide and an

2. High manufacturing cost

inerting gas

3. Provides a poor distribution of

2. Several non-productive

ethylene oxide when the

steps in the reactor

equivalent weight of the base

sequence that accounts for

polyol is greater than about 800

almost 50% of the reactor

Da.

cycle time

4. Need a different equipment for

3. Long residence time

the separation of catalyst from

(3)

the product
(2)

Total

1.8

18

14

Selected method

So3/air sulfation and the semi batch exthoxylation process for manufacture of sodium lauryl
sulfate. This is because this method is cost effective, possessive more advantages among
and better in the yield of sodium lauryl sulfate. It is also figured out that this method offer
higher quality of product and more sustainable.

Sulfation reactions carry out in gas-liquid contact reactors SO3 from sulfur. SO3/air
in gas-liquid contactor (sulfonator) is becoming the predominant process for the
manufacture of anionic surfactants. Adaptability which is primary alcohols can be
successfully transformed to high-quality sulfonate/sulfate active detergents using SO3/air as
sulfonating reagent.

In safety part, Sulfur, either in liquid or solid form, although less dangerous option as
initial material for the manufacture of SO3, is still risky. For price SO3 obtained directly from
the sulfur combustion is the most economical option among all the others options mentioned
above regarding transport, handle and storage. Air/SO3 process are capable of sulfating or

22
sulfonating a wide variety of feedstocks and producing excellent quality products from all of
them.

The choice of sulfation process is the required production capacity. The air/SO3
process is a large scale continuous process best suited to 24 hours per day, seven days per
week manufacture of tons per hour of product. Reagent cost may have a major impact on
choosing a process. The air/SO3 process has the lowest cost per pound of SO3 reacted.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 final factor to consider in the choice of sulfation processes is the cost of waste
disposal. The chlorosulfuric acid process produce large by-product streams of hydrochloric
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 equipment can be costly and the disposal costs can be high.

The air/SO3

process has rapidly overtaken as the predominate choice. Finally, the air/SO3 process is
capable of making a broad range of very high quality products.

In a continuous neutralizer system, neutralizer combines sulfonic acid or organosulfuric acid with a neutralizing agent, additives, and diluents (water), in dominant bath
neutralization. The result is a solution of neutral active matter (slurry or paste) of the desired
composition and pH. Caustic soda, usually NaOH, is the most common neutralizing agent.
Ethoxylates used in detergents are produced via semi-batch processes utilizing base
catalysis, typically potassium hydroxide (KOH). As such ethoxylates are commodity
materials, the production economics and capability to manufacture the precursors are
important determinants of profitability.

23
1.8.1

Process Details

Figure 1.9: Process Flow Diagram of the selected process

24
The plant was designed to produce 50,000 TPA of SLES with a 70% purity using the four
reactions stated in Table 1.6 below. The main reaction is using sulfation process, which SO3
gas is contacted with liquid lauryl alcohol (LA) to produce sulphated lauryl alcohol (LAS). All
four reactions used in the plant are running on exothermic process where the heat release
will be used back again in heat recovery.

Table 1.6: Reactions in the production of SLES

Reactor

Reactions

Catalytic Converter (CRV-101)

2SO2 + O2

2SO3

Plug Flow Reactor (PFR-101)

C12H26O + SO3

C12H26SO4

Neutralizer (CRV-102)

C12H26SO4 + NaOH

NaC12H25SO4 + H2O

Ethoxylation (CRV-103)

NaC12H25SO4 + 3C2H4O NaC14H29SO5 + C4H8O2

Among the four processes used, only two reactions require the usage of catalyst which are
the catalytic converter (CRV-101) and ethoxylation (CRV-103). The catalyst used are
vanadium pentoxide (V2O5) and potassium hydroxide (KOH), respectively.
Reactor CRV-101, also known as the catalytic converter operates at atmospheric
pressure and temperature of 420C to convert SO2 gas into SO3 gas with excess air and
vanadium pentoxide as catalyst. The reaction is extremely exothermic and temperature
dependent, which careful control of temperature is needed in order to achieve the required
percentage conversion of 98%.

The main reactor, PFR-101, which is used to contact gaseous SO3 with lauryl
alcohol, has a conversion percentage of 97% and operates at 50C and 1 atm. The kinetic
data for the reaction in PFR-101 are tabulate in table 1.7 below. The product stream is then
fed into the 3-phase separator (V-101) where the unreacted LA is then recycled back into
the reactor, PFR-101. The product formed, LAS is then fed into the neutralizer unit (CRV102) at 50C where it will produce sodium lauryl sulphate (SLS). The unit operates at 1 atm
and 100C, which is why the by-product came out from the reactor as water vapour. The
product is then heated to 135C prior to be fed into another 3-phase separator (V-102) to
separate the unreacted sodium hydroxide and the SLS in slurry form.

25

Table 1.7: Kinetic data for reaction in Sulfation Process

k = A * exp (-E/RT) * T^b
A

1.55

65

2.4

CRV-103 which is the ethoxylation unit is the last reactor in the production of SLES.
This is the only reactor that operates at above atmospheric pressure of 5 bar and 150C.
Pure ethylene oxide in gaseous form is fed into the reactor after being compressed by a
compressor to achieve the desire pressure of 5 bar. The gas is then contact with SLS with
the presence of KOH catalyst to produce the end product of SLES with 70% purity. The
ethylene oxide, mainly because of its high cost, need to be recycled back into the reactor to
minimize losses and to maximize the utilization of the raw materials. The by-product, 1,4dioxane, however, need to be treated before it can be released as it is harmful and
carcinogenic. The two components are split using a separator (V-103) at 1 atm and 65

26
REFERENCES
The Chemithon Corporation, Application of Pilot Studies to Minimizing 1,4-Dioxane
Production During Sulfonation of Ethoxylated Alcohols, 1988
Foster, N.C., Rollock, M.W., Medium to Very High Active Single Step Neutralization,
Chemithon Corp., U.S.A. (1997).

Hreczueh, W., Miszkiewicz, W., Szymanowski, J., Zimoch, J., and Jerzykiewicz, A.;
High Ethoxylated Alcohols with Narrow Distribution of Homologues; J. Chem.
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Santacesaria, E., Serio, M., and Lisi, L.; Kinetics of Nonylphenol Polyethoxylation
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Serio, M., Tesser, R., Felippone, F., and Santacesaria, E.; Ethylene Oxide Solubility
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Herman de Groot, Sulphonation Technology in the Detergent Industry, Kluwer Academic

Publishers, Dordrecht, The Netherlands, 1991, p. 5.

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surfactant manufacture. Org. Process Res. Dev., Vol.7, No. 2, pp.172-184, ISSN 1520-586X

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Roberts, D. W. (2007). The origin of colour formation in methyl ester sulfonation.
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Torres, J. A., Daz, L., & Snchez, F. J. (2008a). Kinetic study of the sulfonation of methyl
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Torres, J. A., Daz, L., & Snchez, F. J. (2009a). Falling film reactor for methyl ester
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APPENDIX