1

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

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 Molecular formula Molar mass CAS number Appearance Boiling point Melting point Specific gravity Vapour density

Magnesium lauryl sulphate Mg(CH3(CH2)11OSO3)2 278.56g/mol 3097-08-3 Liquid 174.4oC -46oC 0.935 6.2 Source: LookChem 2007

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).

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: IIt is used in pesticides in preventing, destroying, repelling, or mitigating any pest. IIIIIIt is used in the production of soap that is used in daily life. It act as a base for ceramic tiles adhesives, for wood and general purpose adhesives in building industry IVIt is a cleaning agent used in contact lens solution

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.

Global Fatty Acid Production Capacity Production Capacity(million tonnes) 8 7 6 5 4 3 2 1 0 America Europe Area Asia Total 1999 2000 2001 2002 2003 2006

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.

Demand (million tons)

Graph Of Demand Of Chemicals Against Years

Years

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

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.

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 Carbone Scientific Co.Ltd Molekula Ltd. Eurolabs Limited UK Green Scientific Co.Limited Honest Joy Holdings Limited 2A Pharmachem USA Chemical Land21 Shanghai New Union Textra Import & Export Co. Ltd Nanjing Chemlin Chemical Co.Ltd Beijing Tianli Biological Chemical Co.Ltd Location United Kingdom United Kingdom United Kingdom United Kingdom USA USA South Korea China China 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

10

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

11

(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.

12

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) (Lauric acid) (Methanol) CH3(CH2)10COOCH3(l)+ H2O(l) (3.1) (Methyl Laureate) (Water)

(ii)Hydrogenation of Methyl laureate (CuCr) (Copper Chromite) CH3(CH2)10COOCH3(l) + 2H2(g) (Methyl Laureate) (Hydrogen) CH3(CH2)11OH(l) + CH3OH(l) (3.2) (Lauryl alcohol) (Methanol)

13

(iii)Sulfation of Lauryl alcohol

CH3(CH2)11OH(l) + SO3(g) (Lauryl alcohol) (Sulphur trioxide)

CH3(CH2)11OSO3H(l) (Lauryl sulphate)

(3.3)

(iv)Mixing of Lauryl sulphate with Magnesium hydroxide

2CH3(CH2)11OSO3H(l) + Mg(OH)2(aq) (Lauryl sulphate)

Mg (CH3(CH2)11OSO3)2(l) + 2H2O(l) (3.4) (Magnesium lauryl sulphate) (Water)

(Magnesium hydroxide)

14

3.2

BLOCK DIAGRAM

Esterification of Lauric Acid and Methanol

Catalyst = Sulphuric Acid, H2SO4

Hydrogenation of Methyl Laureate

Catalyst = Copper Chromite, CuCr

Sulphation of Lauryl Alcohol

Sulphating Agent = Sulphur Trioxide, SO3

Mixing Lauryl Sulphate with Magnesium Hydroxide

Magnesium Lauryl Sulphate Collected

15

3.3

DESCRIPTION OF PROCESS FLOW

(i)Esterification of Lauric acid and Methanol H2SO4 (Sulphuric acid) CH3(CH2)10COOH(l) + CH3OH(l) (Lauric acid) (Methanol) CH3(CH2)10COOCH3(l) + H2O(l) (3.5) (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) (Methyl Laureate) (Hydrogen) CH3(CH2)11OH(l) + CH3OH(l) (3.6) (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 hydrogen gas (20-25moles) through preheater (E107) before passing through the fixed

16

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) (Lauryl alcohol) (Sulphur trioxide)

CH3(CH2)11OSO3H(l) (Lauryl sulphate)

(3.7)

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 4550oC. A reaction yield of 97% is achieved.

(iv)Mixing of Lauryl sulphate with Magnesium hydroxide

2CH3(CH2)11OSO3H(l) + Mg(OH)2(aq) (Lauryl sulphate)

Mg (CH3(CH2)11OSO3)2(l) + 2H2O(l) (3.8) (Water)

(Magnesium hydroxide) (Magnesium lauryl sulphate)

17

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.

18

19

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) (Lauric acid) (Methanol) CH3(CH2)10COOCH3(l)+H2O(l) (3.9) (Methyl Laureate) (Water)

(ii)Hydrogenation of Methyl laureate CuCr (Copper Chromite) CH3(CH2)10COOCH3(l) + 2H2(g) (Methyl Laureate) (Hydrogen) CH3(CH2)11OH(l) + CH3OH(l) (Lauryl alcohol) (Methanol) (3.10)

(iii)Sulfation of Lauryl alcohol

CH3(CH2)11OH(l) + SO3(g) (Lauryl alcohol) (Sulphur trioxide)

CH3(CH2)11OSO3H(l) (Lauryl sulphate)

(3.11)

(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) (Water)

(Lauryl sulphate) (Magnesium hydroxide) (Magnesium lauryl sulphate)

20

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 shelflife 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)

21

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) The carbon monoxide and hydrogen is then combined to form methanol . (3.15)

22

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 Lauric Acid CH3(CH2)10COOH

Physical Properties Molar mass CAS number Appearance Boiling point Melting point

Property Values 200.32 g/mol 143-07-7 White powder 298.9 C 43.2 C 32.04 g/mol 67-56-1 Liquid 64.6 C -97 C 80.06 g/mol 7446-11-9 Liquid 45 C 16.8 C

Methanol CH3OH

Molar mass CAS number Appearance Boiling point Melting point

Sulphur Trioxide SO3

Molar mass CAS number Appearance Boiling point Melting point

23

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

25

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,

26

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 substances 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

27

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

28

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 selfrescue 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 workers 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) (5.1) (Lauric acid) (LA) (Methanol) (M) (Methyl Laureate) (ML) (Water) (W) CH3(CH2)10COOCH3(l) + H2O(l)

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 =?

Reactor X= 0.9

NoLA=? NoM=? NoW=? NoML=16 kmole/h

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.

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Mass flow rate of methyl laureate (ML) :

3 year

kg

year months

month 3 days

day 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 -1 Methanol -1 Methyl Laureate 1 Water 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.

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Estimated conversion = 0.9 Estimated mole flow rate of methyl laureate =

3 h 3 h g kg mole .3 g mole .3 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+r 16 = 0+(1)r r = 16 kmole/h (b) Water, No=Ni+r =0+(1)(16) =16 kmole/h

(c) Lauric Acid, No=Ni+r Conversion, X=

Ni-No Ni

XNi= Ni-No

33

XNi= -r (0.9)Ni= -(-1)(16) Ni=18 kmole/h No=Ni+r =18 + (-1)(16) =2 kmole/h From equilibrium constant: Ke= (Nik + kr)k =
(Ni (Ni ( ( + + )( ) ) r) r) (Ni + r) (Ni + r)

) (Ni )

4.4 =

( )(Ni -

NiM = 45 kmole/h

(d) Methanol, No=Ni+r No= 45 + (-1) (16) = 29 kmole/h

34

To determine the limiting reactant, For lauric acid (LA) =

Ni kmole h -(- )

= 18 kmole/h For methanol (M) =

Ni kmole h - (- )

= 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 = =

Ni NiT 3

= 0.2857

35

Methanol, xiM =

Ni NiT 3

= 0.7143 Composition of output components:

Lauric acid, xoLA = =

No NoT 3

= 0.0317 Methanol, xoM = =

No NoT 3

= 0.4603 Methyl laureate, xoML= = = 0.2540 Water, xoW = =

No NoT 3 No NoT

= 0.2540

36

Mass flow rate for input components : 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 Methanol Methyl Laureate Water Total

18 45 0 0 63

2 29 16 16 63

Table 5.3: Mass Flow Rate (kg/h) Components Fin(kg/h) Fout(kg/h)

Lauric Acid Methanol Methyl Laureate Water Total

3606 1442 0 0 5048

401 929 3430 288 5048

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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.

NiLA= 18 kmole/h NiM= 45 kmole/h

Reactor X= 0.9

NoLA= 2 kmole/h NoL NoM= 29 kmole/h NoML= 16 kmole/h NoLA= 16 kmole/h

Figure 5.2: Block Diagram For Esterification.

Esterification of Lauric Acid and Methanol H2SO4 (Sulphuric acid) CH3(CH2)10COOH(l) + CH3OH(l) (Lauric acid) (LA) (Methanol) (M) CH3(CH2)10COOCH3(l) + H2O(l) (5.2) (Methyl Laureate) (ML) (Water) H2O

The Cp value of each inflow and outflow component is determined by using: Cp= A + BT + CT2 + DT3 (J/mol.K)

39

Table 5.4: Heat Capacity of Liquid A 50.801 13.431 77.645 8.712 B 2.258 -51.2810-3 2.5348 1.2510-3 C -4.96610-3 131.1310-6 -5.948910-3 -0.1810-6 D 4.37710-6 5.68210-6

Lauric Acid Methanol Methyl Laureatae Water

Table 5.5: Hof of Formation Hof(kj/mol) -682.00 -238.66 -693.42 -285.83

Lauric Acid Methanol Methyl Laureate Water

The change of enthalpy, H of each inflow and outflow component is determined by using:

H=

3 3. .

Cp dT

H= A( T2 - T1 ) + B( T22 - T12 )/2 + C( T23 - T13 )/3+D( T24 - T14)/4

For inflow components: Lauric Acid (LA), H =

3 3. .

Cp dT

= ( 50.801)(313.15-298.15) + (2.258)( 313.152-298.152) /2 + (-4.966x10-3)( 313.153-298.153)/3 + (4.377x10-6)( 313.154-

40

298.154)/4 = 6030 kJ/mol Methanol (M), H =

3 3. .

Cp 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 =

3 3. .

Cp 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)( 393.154298.154)/4 = 39748 kJ/mol Methanol (M), H =
3 3. .

Cp dT

= (13.431)( 393.15-298.15) + (-51.28x10-3)( 393.152-298.152) /2 +(131.13x10-6)(393.153-298.153)/3

41

= 9061 kJ/mol

Methyl Laureate (ML), H =

3 3. .

Cp 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)( 393.154298.154)/4 = 45378 kJ/mol

Water (W), H =
3 3. .

Cp 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, Hin = (HiLA x NiLA ) + (HiM x NiM)

42

= ( 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

o - H freactant

= (-693.42kJ/mol 285.83 kJ/mol ) ( -682 kJ/mol 238.66 kJ/mol) = -59 kJ/kmol

Hence, Q = Hout - Hin + rHof = 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

(b) Result For Reactor.

46

47

(c) Result For Output Stream

48

49

Comparison: Mass Balance:

Table 5.6: Result from iCON Total mass balance(kg/h) Inlet Outlet Calculated value(kg/h) 5048 5048 iCON value (kg/h) 5047.45 5047.45 Percentage error(%) 0.01 0.01

Energy Balance:

Table 5.7: Result form iCON Calculated value(J/s) Heat flow rate,Q 526619 293921.0695 iCON (J/s) Percentage error(%) 79

50

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

51

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.

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