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CHAPTER 1
INTRODUCTION
1.1 BACKGROUND
Magnesium lauryl sulphate is also known as magnesium dodecylsulphate. Its
chemical formula is Mg(CH3(CH2)11OSO3)2. It exists in pale yellow liquid, mild odor,
soluble in methanol,acetone and water but insoluble in kerosene. For reactivity profile,
magnesium lauryl sulphate is soluble in water to produce a solution which has pH
value higher than 7.0. It reacts as base to neutralize acid. It usually does not react as
either oxidizing agents or reducing agents but such behaviour is not impossible. It is
combustible.
Figure 1.1 shows the structural formula of magnesium lauryl sulphate.
Figure 1.1 Structural Formula Of Magnesium Lauryl Sulphate
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Magnesium lauryl sulphate is used mainly in industries for the production of
soap, detergents, cosmetic, skin care products, toothpaste, pesticide and others. It is an
anionic surfactant or surface-active agent and has been used widely as an ingredient of
cleaner.
The raw materials for the production of magnesium lauryl sulphate are lauric
acid and methanol. The raw materials undergo four main unit processes, namely
neutralisation, hydrogenation, sulphation and mixing. Methyl laureate will be
produced during the esterification reaction. It is then hydrogenated to form lauryl
alcohol. The lauryl alcohol is then sulphated to form lauryl sulphate before it is mixed
with magnesium hydroxide to form magnesium lauryl sulphate.
Magnesium lauryl sulpahte has its own unique physical properties. Table 1.1
shows the physical properties of Magnesium lauryl sulphate.
Table 1.1 Physical Properties Of Magnesium Lauryl Sulphate
Properties Magnesium lauryl sulphate
Molecular formula Mg(CH3(CH2)11OSO3)2
Molar mass 278.56g/mol
CAS number 3097-08-3
Appearance Liquid
Boiling point 174.4oC
Melting point -46oC
Specific gravity 0.935
Vapour density 6.2
Source: LookChem 2007
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CHAPTER 2
APPLICATION AND ECONOMY
2.1 PRODUCT USAGE
Magnesium lauryl sulfate is made by joining sulfate and lauric acid, two substances
which are both abundant throughout the body. Applications most relevant in terms of
public exposure include it used as a surfactant. Magnesium lauryl sulfate surfactants
consisting of both sulphates straight chain alcohol and fatty alcohol ether sulfate are
available primarily in the lauryl chain length. It is biodegradable. It provides high
foaming even in the present of hard water and exhibit good wetting and emulsifying
properties. Magnesium lauryl sulphate is used in car shampoo, bubble baths, shaving
creams, cleansing creams, industrial cleaner, foams and dust control, liquid household
detergents and others. (Flick, 1993)
Magnesium lauryl sulphate has its own advantages which are have good
foaming properties especially if some unsulfated alcohol is retained in the product.
Surfactant is a chemical compound that possesses great surface activity. Magnesium
lauryl sulphate is a good anionic surfactant which is used to make anionic detergent in
the absence of high water hardness ion such as magnesium ion. However, in the
absence of builders and presence of high water hardness, its effectiveness as cleaners
will be reduced. Magnesium lauryl sulphate has disadvantages and negative impacts
towards environment and daily life. It may cause skin and eye irritation. Hence
combination with other surfactants such as alkanolamides is necessary to lower
irritancy and to deliver desirable qualities (Gervajio, 2005).
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In modern technology, surfactants such as magnesium lauryl sulphate have
replaced soap as a foaming agent in most of the modern toothpaste. It has better
keeping properties are equally effective in either acid or alkaline media and do not
form precipitate of calcium salts with hard water or saliva. Surfactants can be
classified according to their odour and taste, their foaming, emulsifying and cleansing
properties, their stability to acids and alkalis and their compatibility with other
ingredients of the paste. (Board, 2000)
Magnesium lauryl sulfates is used in the carpet cleaner. It functions to pull the
dirt and grime out of the carpet fibre and then dries so that vacuum cleaning can
effectively remove the dirt. Magnesium lauryl sulphate is usually used in the
combination of sodium lauryl sulphate to wet the surface of the fibre where the most
of the dirt is collected. In particular, magnesium lauryl sulphate helps surround the
dislodge dirt into a more friable, dried mass on the surface of the fibre for easily
removal with a vacuum cleaner. (Nelson, 1990)
Cosmetics products are created for application on the body for the purpose of
cleansing, beautifying or altering appearance and enhancing attractive features
Magnesium lauryl sulphate has been included as ingredients for making cosmetic
product. (Flick, 1991). There are also product usages of magnesium lauryl sulfate
which include:
I- It is used in pesticides in preventing, destroying, repelling, or mitigating any
pest.
II- It is used in the production of soap that is used in daily life.
III- It act as a base for ceramic tiles adhesives, for wood and general purpose
adhesives in building industry
IV- It is a cleaning agent used in contact lens solution
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2.2 DEMANDS
Magnesium lauryl sulphate is a chemical which is used in the industries which are
producing soap, shampoo, detergent, cosmetic and skin care products. Its raw
materials are fatty acid, methyl ester, and lauryl alcohol, which both are
oleochemicals.
In Malaysia, the demand of magnesium lauryl sulphate is moderate. The
growth of the demand of magnesium lauryl sulphate in local market is not clear. There
is lack of reliable yet relevant commercial reports or articles to show the growth of the
demand and its production rate. The use of magnesium lauryl sulphate for productions
is not common. Sodium lauryl sulphate is used widely instead.
Based on an article from Indonesian Commercial Newsletter in 2002, the
production rate for oleochemical increased 8% per annum from 526,259 tons in 1997
to 712,012 tons in 2001. In 2001, the annual production capacity of fatty acid is
374,000 tons, 55,900 tons of glycerine, 90,000 tons of fatty alcohol and 10,000 tons of
methyl ester. The production of fatty acid has made 67% of the total production of
oleochemical. Based on the statistics given, the growth of the demand of fatty acid in
Indonesia shows positive sign to the market and it is estimated to be increased in the
following years.
Globally the production of fatty acid shows increment as the demand is
increased. Figure 2.1 shows the global fatty acid production capacity for areas from
1999 to 2006.
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America Europe Asia Total0
1
2
3
4
5
6
7
8
Global Fatty Acid Production Capacity
199920002001200220032006
Area
Pro
du
ctio
n C
apac
ity(
mill
ion
ton
nes
)
Figure 2.1: Global Fatty Acid Production Capacity From 1999-2006.
Source: MPOB, 2005
Fatty acid is the main raw material for the production of magnesium lauryl
sulfate. From the bar chart above, the global fatty acid production capacity is constant
for America and Europe from 1999 to 2006. Meanwhile for Asia, the production
capacity of fatty acid is increased over the years. Overall, the production has increased
from 5 million tones to 7million tones.
As a conclusion, the increasing production of fatty acid from 1999 to 2006 has
given a relationship that the demand of the magnesium lauryl sulfate is also increasing
as its raw material is highly produced.
Most of the application of magnesium lauryl sulphate is in the industry of
cleaner or soap. According to a data from Wikipedia, the demand of soap, detergents
and cleaners shows increment from 1997 to 2007. Figure 2.2 shows the growth of the
demand for chemical products from 1997 to 2007.
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Figure 2.2: The Growth Of The Demand For Chemical Products 1997-2007.
Source: Wikipedia, 2010
The demand for oleochemical products such as soap and detergents are
increased from 1997 to 2007. The graph has clearly shown that the oleochemical
products are needed worldwide in big capacity. There are about 120 million tonnes per
year of soap, detergents and other products produced to meet the huge global demand.
These oleochemical products are derived from oleochemical. Magnesium lauryl
sulphate is the main ingredient for these products. As the demand of the soap and
other oleochemical products is increasing, the demand for the magnesium lauryl
sulphate is also increasing for the production of oleochemical products.
Through Figure 2.1 and Figure 2.2, the raw material of the production of
magnesium lauryl sulphate which is fatty acid has shown increment over the years.
The global demand for oleochemical products such as soap and detergents also
Years
Demand (million tons) Graph Of Demand Of Chemicals Against Years
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increased. Magnesium lauryl sulphate is needed for the production of these
oleochemical products.
Hence an overall conclusion can made that the demand of magnesium lauryl
sulphate is also increased.
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2.3 DEMAND AND SUPPLY
Magnesium lauryl sulphate is mainly produced in Asia due to the growth of the new
modern oleochemical industry. Meanwhile the Europe also playing an important role
for supplying of this chemical. Overall, this chemical is produced mainly from China,
South Korea, USA and United Kingdom. Table 2.1 below shows a list of supplier of
magnesium lauryl sulphate over the countries.
Table 2.1 Supplier of Magnesium Lauryl Sulfate
Company Location
Carbone Scientific Co.Ltd United Kingdom
Molekula Ltd. United Kingdom
Eurolabs Limited United Kingdom
UK Green Scientific Co.Limited United Kingdom
Honest Joy Holdings Limited USA
2A Pharmachem USA USA
Chemical Land21 South Korea
Shanghai New Union Textra Import & Export Co. Ltd China
Nanjing Chemlin Chemical Co.Ltd China
Beijing Tianli Biological Chemical Co.Ltd China
Source: Chemical Book, 2010
The supplier of magnesium lauryl sulphate, UK Green Scientific Co. Limited
is located in United Kingdom. It is a professional company committed to provide the
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best international services to help the global drug discovery develop innovative
medicines and products to treat patients, ease suffering and to enhance the quality of
life. With a strong supplier network combining an advanced information exchanging
platform and world-class services, they offer flexible customer synthesis and bulk
chemicals in a timely, high purity and cost-effective manner with the assurance of
quality and confidentiality. ( Green Scientific, 2010 )
The next company that produce magnesium lauryl sulfate is Nanjing Chemlin
Chemical Industry Co., Ltd. It was established in December of 1999. Business scope
covers Commodity Chemicals, intermediates & fragments and custom synthesis &
manufacture. Their products include bulk commodities, lab agents, intermediates &
fragments, special chemicals, agro-chemicals, APIs, natural ingredients etc., handling
quantity from milligrams to multi-kgs. They have established long-term relation with
various international professional suppliers for many products by way of spot
transaction, agency dealing, or contracted production, and co-developing, etc. With
the rapid growth of this company, they are step-forwarding to set up more cooperation
chance with their clients for mutual interest and benefits. ( TM Chemlin, 2009)
Chemicalland21.com is also one of the companies that produced magnesium
lauryl sulfate which located in South Korea. They aim to be a resource of industrial
chemical information including technical data, safety data, market prices and related
compounds. ( Chemicalland 21, 2008)
Magnesium lauryl sulphate is not a common chemical compared to other fatty
acid alcohol sulphate in the production of several oleochemical industries. Due to its
low popularity, the clear figure of its supply is not available. Qualitatively, the global
production rate of fatty acid (Figure 2.1) and the demand for oleochemical products
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(Figure 2.2) has brought a important message that the demand of the magnesium
lauryl sulphate meet the supply of this chemical.
2.4 FUTURE MARKETING POTENTIAL
Magnesium lauryl sulfate has been used in many industries and household
applications over the years. The chemical is widely use as detergents, lubricants,
surfactants, emulsifier, and also pesticides.
Based on Figure 2.1, the production of fatty acid is increasing from 1999 to
2006. The increasing production is necessary to meet the demand of magnesium lauryl
sulphate. Besides that other oleochemicals such as methyl ester and lauryl alcohol
shown increment in production at 8% per annum. (High Beam Research, 2002).
Based on Figure 2.2, the growth of the demand of oleochemical products
especially soap and detergents has given a good sign to investor on this industry. The
increasing demand of manufactured products and high production of its raw materials
are evidence for a good marketing potential of magnesium lauryl sulphate.
Although it is not as common as sodium lauryl sulphate, there is a space for its
growth. With the references of the statistics shown, the future market for magnesium
lauryl sulphate is positive and prosperous. Investment is necessary for more rapid
growth.
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CHAPTER 3
PROCESS DESCRIPTION
3.1 CHEMICAL REACTION
There are four main reactions for the production of magnesium lauryl sulphate. Raw
material used for the production is lauric acid or dodecanoic acid and methanol. The
processes involved in the production are esterification, hydrogenation, sulfation and
the reaction with magnesium hydroxide. Chemical reactions occurred is shown below:
(i)Esterification of Lauric acid and Methanol
H2SO4
(Sulphuric acid)
CH3(CH2)10COOH(l) + CH3OH(l) CH3(CH2)10COOCH3(l)+ H2O(l) (3.1)
(Lauric acid) (Methanol) (Methyl Laureate) (Water)
(ii)Hydrogenation of Methyl laureate
(CuCr)
(Copper Chromite)
CH3(CH2)10COOCH3(l) + 2H2(g) CH3(CH2)11OH(l) + CH3OH(l) (3.2)
(Methyl Laureate) (Hydrogen) (Lauryl alcohol) (Methanol)
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(iii)Sulfation of Lauryl alcohol
CH3(CH2)11OH(l) + SO3(g) CH3(CH2)11OSO3H(l) (3.3)
(Lauryl alcohol) (Sulphur trioxide) (Lauryl sulphate)
(iv)Mixing of Lauryl sulphate with Magnesium hydroxide
2CH3(CH2)11OSO3H(l) + Mg(OH)2(aq) Mg (CH3(CH2)11OSO3)2(l) + 2H2O(l) (3.4)
(Lauryl sulphate) (Magnesium hydroxide) (Magnesium lauryl sulphate)
(Water)
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3.2 BLOCK DIAGRAM
Esterification of Lauric Acid and Methanol
Hydrogenation of Methyl Laureate
Sulphation of Lauryl Alcohol
Mixing Lauryl Sulphate with Magnesium Hydroxide
Magnesium Lauryl Sulphate Collected
Catalyst = Sulphuric Acid, H2SO4
Catalyst = Copper Chromite, CuCr
Sulphating Agent = Sulphur Trioxide, SO3
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3.3 DESCRIPTION OF PROCESS FLOW
(i)Esterification of Lauric acid and Methanol
H2SO4
(Sulphuric acid)
CH3(CH2)10COOH(l) + CH3OH(l) CH3(CH2)10COOCH3(l) + H2O(l) (3.5)
(Lauric acid) (Methanol) (Methyl Laureate) (Water)
Lauric acid and methanol are the raw materials for the production of
magnesium lauryl sulphate. The two feeds are firstly heated before they are fed into
the reactor (V101). Esterification is occurred in the reactor at 140oC with the presence
of sulphuric acid, H2SO4 as catalyst. Methyl laureate and water are produced from the
reaction. Next the products and unreacted lauric acid and methanol entered fractional
distillation column (D101) where distillation is occurred. Methyl laureate is separated
from the mixture and is pumped to next unit process. Water is a waste which is been
sent out for waste treatment. The unreacted lauric acid and methanol are sent back to
reactor again for more complete reaction.
(ii)Hydrogenation of Methyl laureate
(CuCr)
(Copper Chromite)
CH3(CH2)10COOCH3(l) + 2H2(g) CH3(CH2)11OH(l) + CH3OH(l) (3.6)
(Methyl Laureate) (Hydrogen) (Lauryl alcohol) (Methanol)
Methyl laureate from the distillation tower entered fixed bed reactor (F101)
where catalyst is “fixed” as a bed inside the reactor. The catalyst used is copper
chromite which is in the form of compact pelletized. The reaction in the reactor is
conducted in the vapour phase where part of the feed is vaporised in an excess of
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hydrogen gas (20-25moles) through preheater (E107) before passing through the fixed
catalyst bed reactor (F101). Hydrogenation is occurred in the reactor at pressure
20,000-30,000 kPa and temperature 200-250oC. The reaction mixture leaving the
reactors is cooled and is separated into gas phases and liquid phases. Gas phase
consists mainly hydrogen is then recycled. Liquid phase is expanded into a flash tank
(L101) to strip off methanol from the lauryl alcohol or dodecan-1-ol. The operating
condition is comparatively mild, so that the lauryl alcohol does not require further
processing due to its high quality. Catalyst comsumption is claimed not exceeding
1.0% meanwhile the yield for this fixed bed process is high.
(iii)Sulphation of Lauryl alcohol
CH3(CH2)11OH(l) + SO3(g) CH3(CH2)11OSO3H(l) (3.7)
(Lauryl alcohol) (Sulphur trioxide) (Lauryl sulphate)
Lauryl alcohol is then fed into multitude film sulphation reactor.(F201) The
latest technology in the manufacture of lauryl sulphate is the direct use of sulphur
trioxide gas, SO3 as the sulphating agent. The sulphur trioxide gas from pipeline is fed
into the reactor with lauryl alcohol for sulphation to occur. The feeds entered from the
top section of the reactor and flew concurrently downward inside the tube. As the
reaction is almost instantaneous and exothermic, cooling water at controlled flow is
introduced into the jacket of the reactor to maintain the reaction temperature at 45-
50oC. A reaction yield of 97% is achieved.
(iv)Mixing of Lauryl sulphate with Magnesium hydroxide
2CH3(CH2)11OSO3H(l) + Mg(OH)2(aq) Mg (CH3(CH2)11OSO3)2(l) + 2H2O(l) (3.8)
(Lauryl sulphate) (Magnesium hydroxide) (Magnesium lauryl sulphate) (Water)
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Lauryl sulphate that is produced from sulphation is quite unstable and needed
to be neutralized immediately. Excess SO3 gas is sent to scrubber unit for rectification
and to be reuse. Meanwhile lauryl sulphate is sent to mixer (M101) for homogenous
neutralisation reaction. Magnesium hydroxide, Mg (OH) 2 is fed into the mixer from
pipeline. Magnesium lauryl sulphate is collected.
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3.5 SOURCE OF RAW MATERIAL
Magnesium lauryl sulphate can be produced by serial reactions. There are four basic
processes, include esterification of lauric acid and methanol, hydrogenation of methyl
laureate, sulfation of lauryl alcohol and the reaction between magnesium hydroxide
with lauryl sulphate.
Reactions:
(i)Esterification of Lauric acid and Methanol
H2SO4
(Sulphuric acid)
CH3(CH2)10COOH(l) + CH3OH(l) CH3(CH2)10COOCH3(l)+H2O(l) (3.9)
(Lauric acid) (Methanol) (Methyl Laureate) (Water)
(ii)Hydrogenation of Methyl laureate
CuCr
(Copper Chromite)
CH3(CH2)10COOCH3(l) + 2H2(g) CH3(CH2)11OH(l) + CH3OH(l) (3.10)
(Methyl Laureate) (Hydrogen) (Lauryl alcohol) (Methanol)
(iii)Sulfation of Lauryl alcohol
CH3(CH2)11OH(l) + SO3(g) CH3(CH2)11OSO3H(l) (3.11)
(Lauryl alcohol) (Sulphur trioxide) (Lauryl sulphate)
(iv)Mixing of Lauryl sulphate with Magnesium hydroxide
2CH3(CH2)11OSO3H(l)+Mg(OH)2(aq) Mg(CH3(CH2)11OSO3)2(l)+2H2O(l) (3.12)
(Lauryl sulphate) (Magnesium hydroxide) (Magnesium lauryl sulphate) (Water)
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Based on the reaction above, the raw materials that are used to produce
magnesium lauryl sulphate are lauric acid and methanol. Lauric acid comes from
carboxyl group (carboxylic acid) while methanol comes from hydroxyl group
(alcohol).
3.5.1 LAURIC ACID
Lauric acid is a saturated fatty acid which comes from carboxyl group. It is also
known as dodecanoic acid with molecular formula CH3(CH2)2COOH. It exist as white
and powdery solid with faint odor of bay oil and soap.
Melting point :440C
Boiling point : 298oC
It is steam volatile and dissolve readily in alcohol and ether,but is only very
slightly soluble in water. Lauric acid is the main acid in coconut oil and in palm kernel
oil. It is believed to have antimicrobial properties. It is inexpensive, has a long shelf-
life and safe to handle.
Lauric acid can be obtained by hydrolysis and splitting process of its
triglycerides (coconut oil). Glycerine is the byproduct for this fat splitting process.
Trigyceride (coconut oil) + water fatty acid (lauric acid) + glycerine (3.13)
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The salt and esters of lauric acid are called laureates. Lauric acid is used as a
stabiliser for PVC and as an intermediate for production of softener and emulsifiers
such as magnesium lauryl sulphate. (Wikipedia,2010)
3.5.2 METHANOL
Methanol is the most simple alcohol comes from hydroxyl group. Its molecular
formula is CH3OH.Methanol is light,volatile, colorless, flammable and is liquid with a
distinctive odor that is very similar to but slightly sweeter than ethanol.
Melting point :-97oC
Boiling point : 64.7oC
Methanol can be produced naturally by anaerobic metabolism of bacteria and
is found in small fraction in the atmosphere. Besides, methanol can be produced from
the methane component in natural gas. There are three processes which are
commercially practised.
CH4(g)+ H2O(g) → CO(g) + 3 H2 (g) (3.14)
Syn gas is produced according to the chemical reaction above. The gas is then
pass through a process called shift reaction to adjust the ratio of CO and H2.
CO (g) + H2O(g) → CO2 (g)+ H2 (g) (3.15)
The carbon monoxide and hydrogen is then combined to form methanol .
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CO(g) + 2 H2(g)→ CH3OH (l) (3.16)
Methanol is used in esterification process of fatty acid to form methyl ester.
(Wikipedia,2010)
Table 3.1 shows the physical property of reactants used for the production of
magnesium lauryl sulphate.
Table 3.1: Physical Property Of Reactants
Chemical Reactants Physical Properties Property Values
Lauric Acid
CH3(CH2)10COOH
Molar mass
CAS number
Appearance
Boiling point
Melting point
200.32 g/mol
143-07-7
White powder
298.9 °C
43.2 °C
Methanol
CH3OH
Molar mass
CAS number
Appearance
Boiling point
Melting point
32.04 g/mol
67-56-1
Liquid
64.6 °C
-97 °C
Sulphur Trioxide
SO3
Molar mass
CAS number
Appearance
Boiling point
Melting point
80.06 g/mol
7446-11-9
Liquid
45 °C
16.8 °C
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Magnesium Hydroxide
Mg(OH)2
Molar mass
CAS number
Appearance
Boiling point
Melting point
58.32 g/mol
1309-42-8
White solid
-
350 °C (decomposes)
Source: Sciencelab.com, 2010
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CHAPTER 4
ENVIRONMENTAL AND SAFETY ISSUES
4.1 WASTE GENERATION
Water is produced at the final stage of the chemical reaction. A portion of water is
evaporated during the distillation process. Part of water generated is also used as a
medium for heat to transfer in heat exchanger while the rest is treated before being
discharged. Methanol is used in excess during the esterification of lauric acid and
methanol. It is recycled back to the reactor for future reaction after been fractionated
out from fractional distillation tower. It is also been produced during second stage of
the production, that is hydrogenation where it comes out with lauryl alcohol. The
methanol separated from the product and stored in gasometer.
4.2 IMPACT ON THE ENVIRONMENT
The production process of magnesium lauryl sulfate, as in any other chemical process,
has its own effect on the environment. Studies shows that this production process
could do some damage, especially to the water environment in the long term. When
tested on rat and guinea pig, this chemical shows a high toxicity level. As for human,
the damage can only be seen if contact occurs on a high dosage.
Since the waste is released to the sewerage system, the main pollution concern
is related to the river. More than 90% of the chemical that is released to the river tend
to stay there. So it is a cause for concern. For this particular reason, companies
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producing chemicals has to follow a certain disposing limit. This limit is called
discharge limit.
Discharge limit were designed to protect designated uses of surface waters,
such as supporting aquatic life or recreation. For this particular product, if unaltered
by use, may be disposed of by treatment at a permitted facility or as advised by the
local hazardous waste regulatory authority. Residue from fires extinguished with this
material may be hazardous. Thus, controlling discharge from entering the
environment, particularly the navigable waters, are very important.
To control the waste disposal in Malaysia, an act has been created related to
prevention, abatement, control of pollution and enhancement of the environment. This
act is called Environmental Quality Act 1974.
4.3 RELEVANT ENVIRONMENT ACT
In Malaysia, there are at least two well known act or regulation related closely to this
particular situation and issues. Those two are Environmental Quality Act (1974) and
Environmental Quality Regulations (1979). Following is a more detailed description
of these regulations.
4.3.1 ENVIRONMENTAL QUALITY ACT 1974
The Environmental Quality Act 1974 is under the Act 127, Law of Malaysia. The
section that is related to this particular issue is Section 25 entitled “Restrictions on
pollution of inland waters”. This section stated that “No person shall, unless licensed,
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emit, discharge or deposit any environmentally hazardous substances, pollutants or
wastes into any inland waters in contravention of the acceptable conditions” (Malaysia
Environment, 1974). The existence of this act ensures the chemical processing
company to follow and obey the designated discharge limit that has been stated.
4.3.2 ENVIRONMENTAL QUALITY (SEWAGE AND INDUSTRIAL
EFFLUENTS) REGULATIONS, 1979
Part three of this regulation is about the acceptable condition of discharge into the
inland waters. The following is among the regulations:
1. No inflammable solvent shall be discharge into the inland waters. The same
also goes for any tar or other liquids that is immiscible with water.
2. Effluent that is to be discharge also must be analyzed in accordance to the
specified method (United Nation, 1979)
4.4 SAFETY PRECAUTION
Magnesium lauryl sulfate is a very flammable substance. Inhalation may cause
irritation of the respiratory tract. It is also harmful if swallowed and can cause
difficulty in ingestion. If contact occurs with bare skin, it may cause allergic skin
reaction to some type of skin. Direct contact with eye should also be avoided.
Breathing this substance’s vapours or spray mist would not be a good idea (MP
Biomedical, 2006).
Avoid contact on eyes, skin, or even on clothing. It is advised to wear personal
protective equipment and cloth. After used, remove and wash the contaminated
clothing before reuse. Also, it is best to clean the whole body thoroughly after
handling. For some unfortunate event, if large spills occur, use water to disperse the
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vapour and also avoid the liquid chemicals from entering any waterways or sewer
system.
For transferring purpose, use ground and bond containers. Also, make sure to
keep this chemical away from open flames, hot surfaces or any type of source for
ignition. This particular precaution step should not be taken lightly since it is
flammable. It is best not to re-use empty containers for transferring this chemical.
The first step of the production of magnesium lauryl sulfate is the
etherification process. This process takes place with lauric acid and methanol as the
reactant. Methanol has a very high flammability characteristic (Science Lab.com,
2008). The National Fire Protection Association (NFPA), an international nonprofit
organization has rated methanol a level three on the flammability scale.
During the sulphonation process, sulphur trioxide is used as one of the
reactant. Sulphur trioxide is a very corrosive compound (Science Lab.com, 2008).
Therefore to handle the compound, high grade stainless steel or titanium must be used
in the reactor. The storage tank is constructed of tile-lined steel or concrete. As for
piping, it made of high grade stainless steel, polyvinyl chloride or fibreglass-
reinforced polyester.
In this processing plant there are many pumps, pipes and valve required to make sure
the process run smoothly and in complete condition. When working on pumps, pipes, or
valves there is a high possibility of the liquid being squirt out especially if there is any
damage or leakage occur. The production crew have to wear goggles or a face shield
to prevent direct contact with any of these hazardous chemicals. If there is such
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incident happen the construction crews must know the location of the nearest
emergency shower and eyewash station.
Most of the process involved in this production is operated at a high
temperature. To make sure all the accident in plant process will not occur, the
production crew should be made aware of any emergency procedures that are in place.
If there is an evacuation plan involving special assembly areas or the use of self-
rescue equipment such as respirators, these precautions must be fully explained to all
workers in the plant. The plant should have some kind of alarm system to warn people
of a gas leak or any process problem.
Other self protection equipment includes safety glass with side shields. This
safety equipment would be very useful in the event of any device leakage, since the
liquid chemicals might squirt out directly to the worker’s face. In this case, the regular
safety glass would not be sufficient to cover the eye part.
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CHAPTER 5
MASS BALANCE AND ENERGY BALANCE
5.1 MASS BALANCE
Based on an article from Indonesian Commercial Newsletter in 2002, the production
rate for oleochemical increased 8% per annum from 526,259 tons in 1997 to 712,012
tons in 2001. In 2001, the annual production capacity of methyl ester is 10,000 tons.
According to Equation 5.1, the product of the esterification reaction is methyl laureate
and water.
H2SO4
(Sulphuric acid)
CH3(CH2)10COOH(l) + CH3OH(l) CH3(CH2)10COOCH3(l) + H2O(l)
(5.1)
(Lauric acid) (Methanol) (Methyl Laureate) (Water)
(LA) (M) (ML) (W)
The production rate for esterification reaction is 10,000,000 kg in year 2001. Based on
the increment rate which is 8% per annum, it is estimated that the production of
methyl laureate in year 2010 is 30,000,00 kg. The equilibrium constant for
esterification of lauric acid and methanol is estimated to be 4.4. The percentage of
conversion is estimated 90% (X.L.Hou et al, 2006). Figure 5.1 shows the process flow
diagram for unit process of esterification from iCON® while Figure 5.2 shows the
block diagram for esterification.
30
Figure 5.1: Process Flow Diagram For Unit Process (Esterification)
NiLA=?
NiM =?
Figure 5.2: Block Diagram For Esterification
Assumption: The production is carried out 30 days in every month per year and the
process is operated 24 hours per day.
Mass flow rate of methyl laureate (ML) :
Reactor
X= 0.9NoM=?
NoML=16 kmole/h
NoW=?
NoLA=?
31
¿30000000 kg1 year
×1 year12 months
×1 month30 days
×1 day24 hours
= 3472 kg h-1
The molar mass for input and output components:
Molar mass for lauric acid, MLA = 200.32 g/mole
Molar mass for methanol, MM = 32.04 g/mole
Molar mass for methyl laureate, MML = 214.35 g/mole
Molar mass for water, Mw = 18.02 g/mole
Table 5.1: Stoichiometric Coefficient
Lauric Acid Methanol Methyl Laureate Water-1 -1 1 1
Degree of Freedom Analysis:
Number of unknown =7
Number of independent equation = 4 + 2
Basis = 1
Degree of freedom = 7- (4+2) – 1 = 0.
Estimated conversion = 0.9
32
Estimated mole flow rate of methyl laureate = 3472 kg1h
×1 mole214.35 g
= 3472000 g1 h
×1 mole214.35 g
=16197.80732 m/h
= 16 kmole/h
Estimated equilibrium constant, Ke = 4.4
Mole balance for components:
(a) Methy laureate,
Given No=16 kmole/h
No=Ni+αr
16 = 0+(1)r
r = 16 kmole/h
(b) Water,
No=Ni+αr
=0+(1)(16)
=16 kmole/h
(c) Lauric Acid,
No=Ni+αr
Conversion, X= Ni-NoNi
XNi= Ni-No
XNi= -αr
33
(0.9)Ni= -(-1)(16)
Ni=18 kmole/h
No=Ni+αr
=18 + (-1)(16)
=2 kmole/h
From equilibrium constant:
Ke= Ʃ (Nik + αkr)αk
=
(NiML +αML r) α ML × (Ni W +α W r)α W
(NiLA +αLA r)αLA ×( NiM+ αM r)
α M
= (16 ) (16)
(18-16) (N iM -16)
4.4 = 256(2 )(N iM -16)
NiM = 45 kmole/h
(d) Methanol,
No=Ni+αr
No= 45 + (-1) (16)
= 29 kmole/h
To determine the limiting reactant,
34
For lauric acid (LA) = N iLA-∝LA
= 18 kmole/h-(-1)
= 18 kmole/h
For methanol (M) = N iM-∝M
= 45 kmole/h- (-1)
= 45 kmole/h
Hence, the limiting reactant is lauric acid (LA).
Total input molar flow rate, NiT = NiLA + NiM
= (18 + 45) kmole/h
= 63 kmole/h
Total output molar flow rate, NoT = NoLA + NoM + NoML + NoW
= (2 + 29 + 16 + 16) kmole/h
= 63 kmole/h
Composition of input components:
Lauric acid, xiLA = N iN iT
= 1863
= 0.2857
Methanol, xiM = N iN iT
35
= 4563
= 0.7143
Composition of output components:
Lauric acid, xoLA = N oN oT
= 263
= 0.0317
Methanol, xoM = N oN oT
= 2963
= 0.4603
Methyl laureate, xoML= N oN oT
= 1663
= 0.2540
Water, xoW = N oN oT
= 1663
= 0.2540
Mass flow rate for input components :
36
Lauric acid (LA) FiLA = NiLA × MLA
= 3606 kg/h
Methanol (M) FiM = NiM × MM
= 1442 kg/h
Total input mass flow rate = FiLA + FiM = 5048 kg/h
Mass flow rate for output components :
Lauric acid (LA) FoLA = NoLA × MLA
= 401 kg/h
Methanol (M) FoM = NoM × MM
= 929 kg/h
Methyl laureate (ML) FoML = NoML × MML
= 3430 kg/h
Water (W) FoW = NoW × MW
=288 kg/h
Total output mass flow rate = FoLA + FoM + FoML + FoW = 5048 kg/h
37
Table 5.2 and 5.3 show the results of mole flow balance and mass flow balance in
reactor.
Table 5.2: Mole Flow Rate (kmol/h)
Components Nin(kmol/h) Nout(kmol/h)
Lauric Acid 18 2
Methanol 45 29
Methyl Laureate 0 16
Water 0 16
Total 63 63
Table 5.3: Mass Flow Rate (kg/h)
Components Fin(kg/h) Fout(kg/h)
Lauric Acid 3606 401
Methanol 1442 929
Methyl Laureate 0 3430
Water 0 288
Total 5048 5048
38
5.2 ENERGY BALANCE
From the calculation of mass balance, the mole flow rate for each component is determined. The reactor is assumed non-adiabatic.
NoL
Figure 5.2: Block Diagram For Esterification.
Esterification of Lauric Acid and Methanol
H2SO4
(Sulphuric acid)
CH3(CH2)10COOH(l) + CH3OH(l) CH3(CH2)10COOCH3(l) + H2O(l) (5.2)
(Lauric acid) (Methanol) (Methyl Laureate) (Water)
(LA) (M) (ML) H2O
The Cp value of each inflow and outflow component is determined by using:
Cp= A + BT + CT2 + DT3 (J/mol.K)
Reactor
X= 0.9
NiLA= 18 kmole/h
NiM= 45 kmole/h
NoLA= 2 kmole/h
NoM= 29 kmole/h
NoML= 16 kmole/h
NoLA= 16 kmole/h
39
Table 5.4: Heat Capacity of Liquid
A B C DLauric Acid 50.801 2.258 -4.966×10-3 4.377×10-6
Methanol 13.431 -51.28×10-3 131.13×10-6
Methyl Laureatae
77.645 2.5348 -5.9489×10-3 5.682×10-6
Water 8.712 1.25×10-3 -0.18×10-6
Table 5.5: ∆Hof of Formation
∆Hof(kj/mol)
Lauric Acid -682.00Methanol -238.66
Methyl Laureate -693.42Water -285.83
The change of enthalpy, ∆H of each inflow and outflow component is determined by using:
∆H= ∫298.15
313.15
C p dT
∆H= A( T2 - T1 ) + B( T22 - T1
2 )/2 + C( T23 - T1
3 )/3+D( T24 - T1
4)/4
For inflow components:
Lauric Acid (LA),
∆H = ∫298.15
313.15
C p dT
= ( 50.801)(313.15-298.15) + (2.258)( 313.152-298.152) /2 +
40
(-4.966x10-3)( 313.153-298.153)/3 + (4.377x10-6)( 313.154-
298.154)/4
= 6030 kJ/mol
Methanol (M),
∆H = ∫298.15
313.15
C p dT
= (13.431)(313.15-298.15) + (-51.28x10-3)( 313.152-298.152) /2 +
(131.13x10-6)(313.153-298.153)/3
=150 kJ/mol
For outflow components:
Lauric Acid (LA),
∆H = ∫298.15
393.15
C p dT
= (50.801)(393.15-298.15) + (2.258)( 393.152-298.152) /2 +
(-4.966x10-3)(393.153-298.153)/3 + (4.377x10-6)( 393.154-
298.154)/4
= 39748 kJ/mol
Methanol (M),
∆H = ∫298.15
393.15
C p dT
= (13.431)( 393.15-298.15) + (-51.28x10-3)( 393.152-298.152) /2
41
+(131.13x10-6)(393.153-298.153)/3
= 9061 kJ/mol
Methyl Laureate (ML),
∆H = ∫298.15
393.15
C p dT
= ( 77.645)( 393.15-298.15) + (2.5348)( 393.152-298.152) /2 +
(-5.9489x10-3)(393.153-298.153)/3 + (5.682x10-6)( 393.154-
298.154)/4
= 45378 kJ/mol
Water (W),
∆H = ∫298.15
393.15
C p dT
= (8.712)( 393.15-298.15) + (1.25x10-3)( 393.152-298.152) /2 +
(-0.18x10-6)(393.153-298.153)/3
= 7200 kJ/mol
For total inflow enthalpy, ∆Hin,
42
∆Hin = (∆HiLA x NiLA ) + (∆HiM x NiM)
= ( 6030 kJ/kmol x 18 kmol/h) + (150 kJ/kmol x 45 kmol/h)
= 115290 kJ/h
For total outflow enthalpy, ∆Hout,
∆Hout= (∆HLA x NoLA ) + (∆HM x NoM) + (∆HoML x NoML) + (∆HoH2O x NoH2O)
= (9061 kJ/kmol x 2 kmol/h) + (39748kJ/kmol x 29kmol/h) +
(45378kJ/kmol x 16 kmol/h) + (7200 kJ/kmol x 16 kmol/h)
= 2012062 kJ/h
For Heat of formation in the reactor, Hof
= ∑∆Hofproduct - ∑∆Ho
freactant
= (-693.42kJ/mol – 285.83 kJ/mol ) – ( -682 kJ/mol – 238.66 kJ/mol)
= -59 kJ/kmol
Hence,
Q = ∆Hout - ∆Hin + r∆Hof
= 2012062 kJ/h – 115290 kJ/h + (16 kmol/h x -59kJ/kmol)
= 526619 J/s
= 526619 W.
43
5.3 RESULT OF ICON® `S SIMULATION
(a) Result For Input Stream
44
45
46
(b) Result For Reactor.
47
48
(c) Result For Output Stream
49
50
Comparison:
Mass Balance:
Table 5.6: Result from iCON ®
Total mass
balance(kg/h)
Calculated
value(kg/h)
iCON® value
(kg/h)
Percentage
error(%)
Inlet 5048 5047.45 0.01
Outlet 5048 5047.45 0.01
Energy Balance:
Table 5.7: Result form iCON®
Calculated
value(J/s)
iCON® (J/s) Percentage
error(%)
Heat flow rate,Q 526619 293921.0695 79
51
CONCLUSION
Magnesium lauryl sulphate is a chemical that is widely used in the health care
industries. Most of world demand of this chemical is going towards the production of
soap, shampoo, detergent, cosmetic and skin care products. In Malaysia, the demand
of magnesium lauryl sulphate is at a moderate level. Most of the production company
prefer to use sodium lauryl sulphate instead of magnesium lauryl sulphate due to its
availability. Sodium lauryl sulphate is also more popular because it is safer to use and
yields minimum health hazard. As for the global market, Brazil has been recorded as
the main contributor for the health care products, which is the main usage for
magnesium lauryl sulphate. Based on the global market trend, it can be said that this
chemical substance would have increasing demand in the near future.
The production of magnesium lauryl sulphate required lauric acid (or
commonly known as fatty acid) and methanol as the main raw material. As for the
waste generated from the production process, there is only a small amount of water.
The high purity of water that is released to the sewage system makes this process as an
environmental friendly process. However the constant release of the waste water
would pollute the aquatic environment in the future as a long term effect. So to reduce
the possibility of this from happening, a good prevention plan would be necessary.
The production plant should consider other method of discharging the waste water
instead of just releasing it to the river. By building a waste water treatment facility, the
water generated would have a better place to be released to. This will at least reduce
the possibility of the aquatic environment being polluted in the near future.
The mass and energy balance calculation for the first process has also been
included. Most of the research has been done through internet search and discussion
with the lecturers and among fellow students. Manual search through books at the
library has also been conducted. Magnesium lauryl sulfate has a wide range of
52
application, but most of the demand comes from the cosmetic and personal care
industry. The mass balance equations result at the reactor is 5048 kg/h. The factors
that influence rate are the concentration difference and also the molecular distance.
For the energy balance equation, the result at the reactor is 526619 J/s. Factors that
influence the heat transfer rate is the temperature gradient, phase material, and the
surface area. These results have been compared with the result obtained from the
calculation using iCON®, which is 293921.0695 J/s. The percentage error obtained
when these two values was compared is 79%.
Magnesium lauryl sulphate could be an important chemical in the future. The
increasing trend shows that it has gaining popularity among the personal care
production company. Given a good solution can be found to prevent the production
process from damaging the environment, magnesium lauryl sulphate would have a
bright future and a good potential. Less environmental effect and lesser in production
cost would be a high plus.
53
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