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1 CHAPTER 1

COMPANY PROFILE

1.1

COMPANY LOGO

1.2

BACKGROUND

1.2.1

Origin

Chemicopr Sdn. Bhd. was incorporated June 6, 2000 in Tanjung Langsat, Johor, Malaysia. The goal of the new business was to invest in setting a chemical plant of the production of Butyl Glycol Ether Ethyl. This company has designed all the equipments that related to the processes for the large-scale chemical industry of the production of Butyl Glycol Ether with high productivity in economic and safer ways with minimum production rate of 100,000 matrix tonne/year. Ethylene Glycol Butyl Ether is highly demand by many countries because of its uses such as for both water and solvent-based coatings and industrial and consumer cleaners. Cleaners made with Ethylene Glycol Butyl Ether can remove oils, fats, waxes, greases and baked-on or ground-in residues from floors, walls, glass, metal parts, and equipment. Cleaning products which may contain Ethylene Glycol Butyl Ether include general surface cleaners, floor strippers, window cleaners, spot cleaners, rust removers and ink and resin removers. Paints and coatings that use Ethylene Glycol Butyl Ether range from lacquers, varnishes and enamels to water-based coatings and inks.

2 1.2.2

Support for the Research Community

Chemicorp is committed to the advancement of scientific research and we focus our product development on the introduction new and innovative process to increase our production rate for the market. A key step in the generation of those ideas is our attendance at meetings and conferences. One of the ways that Chemicorp honours their ongoing commitment to the research community is via their support of young engineers. We offer travel funds and support to graduate and post-doctoral students pending approval of their support request. While we can't guarantee funding of all of the requests, we have already donated many thousands of money directly to support the attendance of young engineers at important meetings. 1.2.3

Today

Although Chemicorp has changed over the years, we remain firmly committed to our original goal of providing high quality, affordable products to our customers worldwide. In recent years we have expanded upon our core product lines to include Diethylene Glycol Butyl Ether, Triethylene Glycol Butyl Ether, TetraEthylene Glycol Butyl Ether and others. However, as we grow to meet the needs of our customers we remain committed to our origins and vision. To provide our customers the affordable and highquality products. Today, Chemicorp employs 247 people, with a significant international presence. More than 4,298 products are manufactured and exported from the Tanjung Langsat site.

3 CHAPTER 2

INTRODUCTION

2.1

MANUFACTURING

The principle of monoalkyl ether formation of glycols is called ethoxylation of alcohol or alcoholysis of ethylene oxide. The manufacturing process is similar to the hydration of ethylene oxide to produce ethylene glycols. The process involves the reaction of ethylene oxide with alcohols to form Butyl Glycol Ether and the most frequently used alcohols are methanol, ethanol and n-butanol (Weissermal and Arpe, 1978).

The present invention provides a method for producing a Butyl Glycol Ether, which comprises reacting an alkylene oxide with an alcohol in the presence of a catalyst. In this production, alkylene oxide use is ethylene oxide and the alcohol is nButanol. Presence of catalyst is important because the catalyst is an anion exchange resin which comprises, as the substrate, a polymer of a vinyl aromatic compound and which has a structure such that a quaternary ammonium group is bonded to the aromatic group via a linking group having a chain length of at least 3 and the catalyst use is Sodium Hydroxide.

The primary product of this process is Butyl Glycol Ether (BGE) while the secondary products, di-, tri- and higher ethylene glycol. The secondary products are formed when the primary product and higher Butyl Glycol Ether reacted with the excess ethylene oxide.

4 2.2

PRODUCT AND BY-PRODUCT

2.2.1

Ethylene Glycol Butyl Ether (EGBE)

Butyl Glycol Ether (BGE) is a key ingredient in hundreds of products ranging from industrial and consumer cleaning solutions to water- and solvent-based paints and coatings. Butyl Glycol Ether‟s popularity stems from several special performance characteristics that also provide economic value. Butyl Glycol Ether has been tested extensively to assess health and environmental safety. There is one reaction that is commercially recommended for today‟s production. The reactions reactants are ethylene oxide and alcohol in liquid phase which reacts under suitable temperature, pressure and with the presence of selected catalysts. The reaction between ethylene oxide and alcohol was first discovered in German during World War II. When Butyl Glycol Ether is manufactured from ethylene oxide and n-butanol, other glycol ethers such as the di- and triethylene glycol ethers are produced. Consequently, commercial Butyl Glycol Ether may contain small concentrations of other glycol ethers, n-butanol and ethylene glycol. Then, a stabilizer,

2,

6-bis

(1,

1-dimethylethyl)-4-methylphenol,

can

be

added

at

approximately 0.01% to prevent the formation of peroxides.

a)

Chemical Name and Others Name

Ethylene Glycol Butyl Ether (EGBE) belongs to a group of chemicals known as glycol ethers, which are compounds formed by reacting an alcohol with an alkyl oxide such as ethylene or propylene oxide. Butyl Glycol Ether is one of the monoalkyl ethers, which have the general formula R-O-R‟-OH, where R is an alkyl group, for example, methyl (CH3), and R‟ is - CH2CH2- for the ethylene glycol monoalkyl ethers and CH2CH2CH2- for the propylene glycol monoalkyl ethers. The glycol ethers are liquids which are miscible with water and most organic solvents, so they are widely used as solvents and in cleaners, paints and inks.

The chemical name and from IUPAC Systematic Name, it is called Butyl Glycol Ether. Besides that, it also have other names or synonyms name like Butoxyethanol; β-butoxyethanol; n butoxyethanol; 2-n-butoxyethanol; 2- butoxy-1ethanol; 2-n-butoxy-1-ethanol; O-butyl ethylene glycol; butylglycol; butyl monoether glycol; EGBE; ethylene glycol butyl ether; ethylene glycol n-butyl ether; ethylene glycol monobutyl ether; ethylene glycol mono-n-butyl ether; glycol butyl ether; glycol

5 monobutyl ether; monobutyl ether of ethylene glycol; monobutyl glycol ether; 3-oxa-1heptanol, 2-Butoxyethanol. b)

Molecular and Structural Formula

The molecular formula is C6H14O2. The molecular weight is 118.2. The structural formula is CH3CH2CH2CH2OCH2CH2OH

Figure 2.1: Flat structure of Butyl Glycol Ether

c)

Trade Names

Butyl glycol Ether is known commercially under the following trade names:

1. Butyl Cellosolve® 2. Butyl Icinol® 3. Butyl Oxitol® 4. Dowanol EB® 5. Ektasolve EB® 6. Gafcol EB® 7. Glycol ether EB® 8. Jeffersol EB® 9. Poly-Solv EB®.

Glycol ethers can be derived and also as raw material in production of many chemical compounds. Glycol ethers also can be oxidized to aldehydes and an acid, dehydrated to vinyl ethers, esterifies with usual reagents to form a further useful series of solvents, and converted into the usual series of alcohol derivatives. This compound will react with an aldehyde or ketone will give respective acetal or ketal. (McKetta and Cunningham, 1984)

6 d)

Physical Properties

Butyl Glycol Ether is a colourless liquid with an unpleasant odour. The odour threshold is 0.10 ppm stated by NIOSH in 1990. Conversion factor which is for vapour is 1ppm = 4.9 mg/m3 (20°C, 1014 kPa). e)

Hydrolysis:

Butyl Glycol Ether is unlikely to hydrolyse as alcohols and ethers are generally resistant to hydrolysis (Howard et. al, 1993).

f)

Adsorption/Desorption:

A Koc of 67 indicates that Butyl Glycol Ether will not partition into organic matter contained in sediments and suspended solids, and should be highly mobile in soil (Howard et. al, 1993).

g)

Surface Tension:

Butyl Glycol Ether is surface active, thereby increasing its adsorption potential. Butyl Glycol Ether is soluble in water and most organic solvents. It undergoes reactions typical of glycol ethers (Dow Chemical, 1990): i.

Oxidation to 2-butoxyacetic acid.

ii.

Acetal formation when reacted with aldehydes under acidic conditions.

iii.

Ester formation when reacted with a carboxylic acid, for example, acetic acid, in the presence of a strong acid.

iv.

Phosphate and sulphate esters when reacted with phosphoric and sulphuric acids respectively.

v.

Dehydrogenation

in

the

presence

of

copper

at

high

temperatures. 2.2.2

Diethylene Glycol MonoButyl Ether (DEGBE)

a) Chemical Name and Others Name Diethylene glycol butyl ether (DEGBE) is a type of glycol ether. It is primarily used as a solvent in coatings, inks, cleaners and specialty fluids, or to produce diethylene glycol butyl acetate. It evaporates slowly and is completely water soluble. Other

7 names for DEGBE are Diethylene glycol butyl ether (DGBE), Diglycol monobutyl ether, 2-(2-Butoxyethoxy) ethanol, Butyl CARBITOL™ solvent, Butoxydiglycol and Butyl diglycol ether. Diethylene Glycol MonoButyl Ether solvent is a clear, liquid with a mild ether odour. It evaporates slowly and is completely water soluble.

b) Molecular and structural formula The molecular formula is C8H18O3. The molecular weight is 162.2. The structural formula is C4H9OCH2CH2OCH2CH2OH (Boatman, R.J.et.al, 2001)

8 2.2.3

Triethylene Glycol MonoButyl Ether (TEGBE)

a) Chemical Name and Others Name Triethylene Glycol MonoButyl Ether have several names such as 2-(2-(2butoxyethoxy)ethoxy)ethanol, Butoxytriglycol, 3,6,9-trioxatridecan-1-ol, Butyltriglycol, Triethylene glycol n-butyl ether and Butoxytriethylene glycol. TEGBE is a colourless liquid with a mild odour that is completely soluble in water. TEGBE has a low volatility which means it doesn‟t evaporate easily. The major use of TEGBE is in automotive brake fluid formulations. Other possible uses including as a low-volatility component in paint stripping formulations, dye carrier for textile dye processes, chemical process solvent, chemical intermediate, and household and industrial cleaning formulations. b) Molecular and structural formula The molecular formula is C10H22O4. The molecular weight is 206.28. The structural formula is HOCH2CH2OCH2CH2OCH2CH2OCH2CH2CH2CH3 (Boatman, R.J.et.al, 2001)

9 2.2.4

Tetraethylene Glycol MonoButyl Ether (TetraEGBE)

There is two grades of TetraEGBE which are Tetraethylene Glycol MonoButyl Ether regular grade and Tetraethylene Glycol MonoButyl Ether, high-purity grade, which is designed for high-purity specifications in applications such as polyester resins, UVcurable resins and plasticizers. Tetraethylene Glycol MonoButyl Ether features a higher boiling point and lower volatility than the lower ethylene glycols. It is completely miscible with water and a wide range of organic solvents, but has only a very slight affinity for certain aliphatic hydrocarbons.

10 Table 2.1 - Typical Glycol Ethers (Source: Priority Existing Chemical Number, 1996) Class

Name

Alkyl

Structural.

Formula CAS No

Ethylene Glycol Ethers: Monoalkyl

2-Methoxyethanol

Methyl

CH3-O-CH2-CH2-

2-Ethoxyethanol

Ethyl

OH

2-Butoxyethanol

Butyl

C2H5-O-CH2-CH2-

2-Phenoxyethanol

phenyl

OH

1,2-Dimethoxyethane

methyl

C4H9-O-CH2-CH2OH C6H5-O-CH2-CH2OH CH3-O-CH2-CH2-OCH3

Dialkyl

Trialkyl

2,(2-Methoxyethoxy)ethanol

methyl,

CH3-(O-CH2-CH2)2-

2-(2-n-Butoxyethoxy)ethanol

ethyl

OH

Bis(2-methoxyethyl)ether

ethyl,

C4H9-(O-CH2-

butyl

CH2)2-OH

methyl,

CH3-(O-CH2-CH2)2-

ethyl

O-CH3

2-[2-(2-Ethoxyethoxy)ethoxy]ethanol

ethyl,

C2H5-(O-CH2-

2,5,8,11-Tetraoxadodecane

ethyl,

CH2)3-OH

ethyl

CH3-(O-CH2-CH2)3-

methyl,

O-CH3

109-864 110-805 111-762 122-996 110-714 111-773 112-345 111-966 112-505 112-492

ethyl, ethyl

Propylene Glycol Ethers:

Dialkyl

Monoalkyl 1-Ethoxy-2-propanol

Ethyl

CH3-CH(OH)-CH2-

1569-

1-Butoxy-2-propanol

Butyl

O-C2H5

02-4

2-Methoxypropanol-1

Methyl

CH3-CH(OH)-CH2-

5131-

O-(CH2)3-CH3

66-8

CH3-CH(O-CH3)-

1589-

CH2-OH

47-5

(2-Methoxymethylethoxy)-propano

methyl,

CH3-(O-C3H6)2-OH

34590-

(2-Ethoxy-methylethoxy)-propanol l

propyl

C2H5-(O-C3H6)2-OH

94-8

11

Trialkyl

[2-(2-

ethyl,

300025-

propyl

38-8

methyl,

Methoxymethylethoxy)methylethoxy]- propyl, propanol

propyl

CH3-(O-C3H6)3-OH

2549849-1

12 Table 2.2: Physical Properties of EGME, DEGME, TEGME, and TetraEGME (Source: McKetta and Cunningham, 1984)

Property

Molecular Weight

Butyl Glycol

Diethylene

Triethylene

Tetraethylene

Ether

Glycol

Glycol

Glycol

MonoButyl

MonoButyl

MonoButyl

Ether

Ether

Ether

162.2

206.28

250.3

118.2

o

Boiling point ( C at 1 atm)

b

171.2

230.4

276

304

Flash point (Tag closed cup, oF)

141

230e

250d.e

166

o

-

-68.1

-47.6

-

0.9019

0.9536

1.0021

1.008

7.50

7.95

8.26

-

1.4193

1.4316

-

1.443

6.4

6.49

10.9

14

0.583

0.546

-

-

Heat of vaporization (Btu/lb at 1 atm)

171

111

-

-

Vapour pressure (mmHg, 20oC)

0.6

0.01

<0.01

-

31.5

33.6

-

3.9x10-4

Freezing Point ( C at 1 atm) o

Specific Gravity (20/20 C) o

Pounds/U.S. gal (20 C) Refractive Index (ηD at 20 oC) o

Viscosity (cP, 20 C) o

o

Specific Heat (cal/g C, 20 C)

o

Surface Tension (dyn/cm, 25 C)

a

Decomposers Decomposers if held at this temperature c Pensky-Martens closed cup d Test method not given, but shoul be Pensky-Martens closed cup e Cleveland open cup, 290oF b

13 2.3

RAW MATERIALS

2.3.1

Ethylene Oxide

Ethylene oxide was first reported in 1859 by the French chemist Charles-Adolphe Wurtz, who prepared it by treating 2-chloroethanol with potassium hydroxide: Cl–CH2CH2–OH + KOH → (CH2CH2) O + KCl + H2O Ethylene oxide has a simple molecular structure with the chemical formula of C2H4O. Ethylene oxide can also known as dimethylene oxide, oxirane, ethane oxide and 1, 2-epoxyethane. Ethylene oxide is a colorless gas with sweet ether like odor in room condition. Because of its special molecular structure, ethylene oxide easily participates in the addition reaction, opening its cycle, and thus easily polymerizes. Ethylene oxide is isomeric with acetaldehyde. It is miscible in water. Ethylene oxide reacts with water, strong acids, alkalis, and oxidizers; chlorides of iron, tin, and aluminum; and oxides of iron and aluminum. (Agency for Toxic Substances and Disease Registry, 2007)

The major application of ethylene oxide is for producing many chemicals and intermediates, such as ethylene glycol, ethanol amines, simple and complex glycols, polyglycol ethers and other compounds. It is also a common gas-phase disinfectant which is widely used in hospitals to sterilize heat-sensitive tools and equipment. Ethylene oxide is industrially produced by direct oxidation of ethylene in the presence of silver catalyst. It is extremely flammable and explosive and is used as a main component of thermo baric weapons, therefore, it is commonly handled and shipped as a refrigerated liquid. Ethylene oxide, also called oxirane, is the organic compound with the formula C2H4O. This colourless flammable gas with a faintly sweet odour is the simplest epoxide, a three-membered ring consisting of two carbons and one oxygen atom.

14 2.3.2

n-Butanol

n-Butanol or n-butyl alcohol also called as biobutanol when being produced biologically is a primary alcohol with a 4-carbon structure and the molecular formula C4H10O. It is one of the groups of "fusel alcohols" which means “bad liquor” from the German, which have more than two carbon atoms and have significant solubility in water. n-Butanol is an intermediate in the production of butyl acrylate, butyl acetate, dibutyl phthalate, dibutyl sebacate and other butyl esters, butyl ethers such as ethylene glycol monobutyl ether, di- and triethylene glycol monobutyl ether and the corresponding butyl ether acetates. Other industrial uses include the manufacture of pharmaceuticals, polymers, pyroxylin plastics, herbicide esters and butyl xanthate. It is also used as diluents or as reactant in the manufacture of urea to formaldehyde and melamine to formaldehyde resins. n-Butanol is used as an ingredient in perfumes and as a solvent for the extraction of essential oils. n-Butanol is also used as an extractant in the manufacture of antibiotics, hormones, and vitamins, a solvent for paints, coatings, natural resins, gums, synthetic resins, dyes, alkaloids, and camphor. Other miscellaneous applications of n-butanol are as a swelling agent in textiles, as a component of brake fluids, cleaning formulations, degreasers, and repellents, and as a component of ore floatation agents, and of wood-treating systems. The production or, in some cases, use of the following substances may result in exposure to n-butanol: artificial leather, butyl esters, rubber cement, dyes, fruit essences, lacquers, motion picture and photographic films, raincoats, perfumes, pyroxylin plastics, rayon, safety glass, shellac varnish, and waterproofed cloth.

15 a) Chemical Name and Others Name Butanol or butyl alcohol can refer to any of the four isomeric alcohols of formula C4H9OH such as n-Butanol, butan-1-ol, 1-butanol, n-butyl alcohol; Isobutanol, 2methylpropan-1-ol, isobutyl alcohol; sec-Butanol, butan-2-ol, 2-butanol, sec-butyl alcohol, tert-Butanol, 2-methylpropan-2-ol, tert-butyl alcohol. It can also refer to butanol fuel, a proposed alternative to gasoline. b) Molecular and structural formula The molecular formula is C4H10O. The structural formula is CH3CH2CH2CH2OH

Figure 2.2: n-butanol, skeletal structure

Figure 2.3: n-butanol, flat structure

16 Table 2.3: Physical Properties of Ethylene Oxide and n-Butanol (Source: McKetta and Cunningham, 1984)

Property

Ethylene Oxide

n-Butanol

C2H4O

C4H10O

Molar mass

44.05 g mol−1

74.122 g/mol

Appearance

colorless gas

colourless liquid

0.882 g/mL, 7.360lbs/gallon

0.8098 g/cm3 (20 °C)

Melting point

−111.3 °C

−89.5 °C, 184 K, -129 °F

Boiling point

10.7 °C

117.7 °C, 391 K, 244 °F

Solubility in water

miscible

7.7 g/100 mL (20 °C)

Refractive index(nD)

-

1.399 (20 °C)

Viscosity

-

3 cP (25 °C)

Dipole moment

-

1.52 D

Molecular formula

Density

17 2.4

IMPURITIES

2.4.1

Monoethylene Glycol (MEG)

Monoethylene Glycol is an organic compound widely used as an automotive anti freeze and a precursor to polymers. In its pure form, it is an odourless, colourless, syrupy, sweet-tasting liquid. Ethylene glycol is toxic, and ingestion can result in death. Ethylene glycol is produced from ethylene (ethene), via the intermediate ethylene oxide. Ethylene oxide reacts with water to produce ethylene glycol according to the chemical equationC2H4O + H2O → HOCH2CH2OH (Monoethylene Glycol)

Reaction 1

This reaction can be catalyzed by either acids or bases, or can occur at neutral pH under elevated temperatures. The highest yields of ethylene glycol occur at acidic or neutral pH with a large excess of water. Under these conditions, ethylene glycol yields of 90% can be achieved. The major byproducts are the ethylene glycol oligomers diethylene glycol, triethylene glycol, and tetraethylene glycol. About 6.7 billion kilograms are produced annually.

2.4.2

Diethylene Glycol (DEG)

Diethylene Glycol (DEG) is an organic compound with the formula (HOCH2CH2)2O. It is a colourless, practically odourless, poisonous, viscous, and hygroscopic liquid with a sweetish taste. It is miscible in water, alcohol, ether, acetone and ethylene glycol. DEG is a widely used solvent.DEG is produced by the partial hydrolysis of ethylene oxide. The resulting product is two ethylene glycol molecules joined by an ether bond. Diethylene glycol is derived as a co-product with ethylene glycol and Triethylene glycol. C2H4O + HOCH2CH2OH → C4H10O3 (Diethylene Glycol)

Reaction 2

18 2.4.3

Triethylene Glycol (TEG)

Triethylene glycol, TEG, or triglycol is a colorless, odorless, viscous liquid with molecular formula HOCH2CH2OCH2CH2OCH2CH2OH. It is used as a plasticizer for vinyl. It is also used in air sanitizer products, such as "Oust" or "Clean and Pure." When aerosolized it acts as a disinfectant. Glycols are also used as liquid desiccants for natural gas and in air conditioning systems. It is an additive for hydraulic fluids and brake fluids and is used as a base for "smoke machine" fluid in the entertainment industry. TEG is prepared commercially as a co-product of the oxidation of ethylene at high temperature in the presence of silver oxide catalyst, followed by hydration of ethylene oxide to yield mono-, di-, tri- and tetraethylene glycols. C2H4O + C4H10O3 → C6H14O4 (Triethylene Glycol) 2.4.4

Reaction 3

Tetraethylene Glycol (TetraEG)

A combustible, hygroscopic, colorless, water-soluble liquid, boils at 327°C; used as a nitrocellulose solvent and plasticizer and in lacquers and coatings. C2H4O + C6H14O4 → C8H18O5 (Tetraethylene Glycol)

Reaction 4

(“CEH Marketing Research Report: Glycol Ethers,” Chemical Economics Handbook, SRI Consulting, July 2004, pages 44 and 48.)

19 Table 2.4: Physical Properties of MEG, DEG, TEG, and TetraEG (Source: McKetta and Cunningham, 1984)

Property

Monoethylene

Diethylene

Triethylene

Tetraethylene

Glycol

Glycol

Glycol

Glycol

C2H6O2

C4H10O3

C6H14O4

C8H18O5

Molar mass

62.07 g mol−1

106.12 g/mol

150.17 g mol−1

194.22 g/mol-1

Appearance

-

colourless liquid

Colorless liquid

Liquid

1.1132 g/cm³

1.118 g/mL

1.1 g/mL

1.12 g/mL

Melting point

−12.9°C

–10.45 °C

-7°C

-4.1oC

Boiling point

197.3°C

244–245 °C

285°C

324oC

Solubility in water

Miscible

miscible

-

-

-

-

1.61 × 10−2 N*s /

-

-

m2

-

-

Molecular formula

Density

Refractive index(nD) Viscosity Dipole moment

-

-

20 2.5

APPLICATION AND USAGE

Ethylene Glycol MonoButyl Ether, di-Ethylene Glycol MonoButyl Ether, Triethylene Glycol MonoButyl Ether and TetraEthylene Glycol MonoButyl Ether have many applications in various areas in current global industries. These products are intermediate products because these products will be used later on to produce the end products. 2.5.1

Ethylene Glycol MonoButyl Ether (EGBE)

Ethylene Glycol MonoButyl Ether has been used for more than half a century. Today it is used extensively in both water- and solvent-based coatings and industrial and consumer cleaners. Cleaners made with Ethylene Glycol MonoButyl Ether can remove oils, fats, waxes, greases and baked-on or ground-in residues from floors, walls, glass, metal parts, and equipment. Cleaning products which may contain Ethylene Glycol MonoButyl Ether include general surface cleaners, floor strippers, window cleaners, spot cleaners, rust removers and ink and resin removers. The use of cleaning products containing Ethylene Glycol MonoButyl Ether has caused concern due to the high potential for occupational and public exposure, reports of adverse health effects in some workers such as irritation of the eyes, nose and throat and the established toxicity of related glycol ethers, like the reproductive toxicity of 2methoxyethanol and 2-ethoxyethanol. Paints and coatings that use Ethylene Glycol MonoButyl Ether range from lacquers, varnishes and enamels to water-based coatings and inks.

When added to cleaners, Ethylene Glycol MonoButyl Ether helps lift soil and keeps it suspended until it can be rinsed or wiped away. Because Ethylene Glycol MonoButyl Ether‟s chemical structure includes ether and an alcohol, it can attack water-insoluble oils and greases and water-soluble stains. Ethylene Glycol MonoButyl Ether thus offers manufacturers a variety of cleaning capabilities, from heavy-duty industrial jobs to milder janitorial and household uses. Because Ethylene Glycol MonoButyl Ether is compatible with both petroleum solvents and water, it is found in a wide-range of coatings from automotive and packaging coatings to wood furniture finishes. It is used widely in water-based industrial paints and coatings.

In household products, Ethylene Glycol MonoButyl Ether uses include glass and tile cleaners, waxes, rust removers and metal polishes. The same properties that allow Ethylene Glycol MonoButyl Ether to dissolve and hold soils and stains in

21 suspension make the compound an effective ingredient in water-based protective paints and coatings. Ethylene Glycol MonoButyl Ether also acts to dissolve or suspend pigments and resins until the coating is applied to surfaces. Once the coating is applied, Ethylene Glycol MonoButyl Ether is designed to evaporate, leaving a uniform, dry finish.

22 2.5.2

Diethylene Glycol MonoButyl Ether (DEGBE)

DEGBE belongs to the group of glycol ethers, which are mainly used as solvents. During 1991 – 1993, the production of DEGBE in the European Union ranged from 20,000 to 80,000 tonnes. DEGBE is produced by the reaction of ethylene oxide and n-butanol with an alkalic catalyst. DEGBE has a wide range of uses as a solvent in paints, dyes, inks, detergents and cleaners. The major function is to dissolve various components of mixtures in both aqueous and non aqueous systems. Nearly 60% of DEGBE in Europe is used in cleaning agents and about 35% in paints and surface coatings. DEGBE is used in cosmetic products in France at a maximum concentration of 9%. DEGBE is not used in food and medicine products. According to the notification to the Commission, DEGBE is used in cosmetic products only as a solvent in hair dyes (Johnson KA et.al, 2002). 2.5.3

Triethylene Glycol MonoButyl Ether (TEGBE)

TEGBE is a colourless liquid with a mild odour and very low volatility. This material is completely soluble in water. Butoxytriglycol contains greater than 85% TEGBE. Minor chemical components are: polyethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol, and Triethylene glycol.

Triethylene Glycol MonoButyl Ether is used as a solvent for nitrocellulose, oils, gums, dyes, soaps, grease, paint removers, metal cleaners, and polymers. It is a coalescent for coatings. It is used in manufacturing plasticizers, cutting and hydraulic oils (particularly brake fluids), pesticide formulations, metal cleaning agents, stabilizers and wood preservation (Boatman, R.J et.al, 2001). 2.5.4

Tetraethylene Glycol MonoButyl Ether (TetraEGBE)

TetraEGBE are used as a reactant in the manufacture of polyester resins. tetraEGBE are produced for use in polyester fiber, films and polyethylene terephthalate (PET) resin production, as well as alkyd resins used in paints. The uses for polyester resins are extremely varied, and include boat and marine, construction materials, automotive and aircraft bodies, luggage, furnishings, appliances, textiles and packaging. Polyester fibers are commonly found in textile applications including clothing and carpets. Polyester films are frequently used in packaging and wraps for consumer goods, as well as video, audio and computer tapes. PET is widely used in the manufacturing of beverage bottles and containers, and other consumer goods packaging. TetraEGBE are commonly used in natural gas hydration and treating

23 applications

to

remove

water

and

impurities.

TetraEGBE

have

excellent

hygroscopicity and low volatility. Because of these characteristics, TetraEGBE may be used directly as a plasticizer or modified by esterification. As a plasticizer, TetraEGBE are used in the manufacture of: i.

Safety glass

ii.

Separation membranes (silicone rubber, polyvinyl acetate, cellulose triacetate)

iii.

Ceramic materials (resistant refractory plastics, molded ceramics)

24 2.6

PROCESS SELECTION Figure 2.1: Description Flow of Process Selection

Process Selection Process 2

Zeolite

Process 1

Anion Exchange Resin

Site Selection Process 3

Selangor          

LDH catalyst

Preliminary process Flow PFD

Material Balance Hysis Energy Balance

Negeri Sembilan

Location respect to marketing area Raw material supply Transport facilities Availability of labours Availability of utilities: Water, fuel, power. Availability of sustainable land Environmental impact and Effluent Disposal Local community consideration Climate Political strategic consideration

Market Analysis    

Johor

Raw Material Supplier Buyer / Market Demand Competitor

Thermodynamic Analysis Physical Properties

Hazard Study / MSDS

25

Process Selection Route Selection Stage

Catalyst Selection Stage

Process 2

Process 1

Process 3

Zeolite

Anion Exchange Resin

LDH catalyst

Figure 2.5: Route Selection Stage and Catalyst Selection Stage There are few methods available to produce 100 000 ton/year of EGBE. In this section, there are few aspects that we need to consider. The most economical process is usually the most favorable process. The following processes are the available manufacturing process to produce the product which is Ethylene Glycol Butyl Ether. 2.6.1

First Process

The reactions with the simultaneously production of higher molecular weight ethylene glycol ether derivatives are analogous to those occurring during the hydration of ethylene oxide. The corresponding reactions for the concurrent production of the mono-, di-, triethylene glycol butyl ethers:

There is a large quantity of data available on the German process for the manufacture of the glycol ethers. The monobutyl, ethyl, and n-propyl ethers of ethylene glycol are manufactured by the continuous reaction of ethylene glycol are manufactured by the continuous reaction of ethylene oxide with the anhydrous alcohol at about 2000C and at 25-45 atm pressure.

26 Reaction 1 Ethylene Oxide

Butanol

Ethylene Glycol Butyl Ether, EGBE

Reaction 2 Ethylene Oxide

EGBE

Diethylene Glycol Butyl Ether. DEGBE

Reaction 3 Ethylene Oxide

DEGBE

Triethylene Glycol Butyl Ether. TEGBE

Reaction 4 Ethylene Oxide

DEGBE

Tetraethylene Glycol Butyl Ether. TetraEGBE

Figure 2.6: Reaction of EGBE, DEGBE, TEGBE and TetraEGBE One volume of ethylene oxide and 6 volume of alcohol are fed to a pressure tower packed with iron raschig rings. Excess of alcohol is used to give the required high ratio of glycol ether: diglycol ether, to control the heat librated in the reactor, and to avoid high concentrations of the ethylene oxide and alcohol is exothermic, about 20-25 kg-cal per g mole of ethylene oxide reacted. The reaction product emerges from the base of the pressure tower and is distilled semi continuously. The alcohol is recycled; the pure glycol and diglycol ethers are isolated by batch fractionation. After removal of excess alcohol, the crude product contains about 85 percent glycol ether, 10 percent diglycol ether, and 2-3 percent polygylcol ethers. The yield of ethers is about 90-95 percent on ethylene oxide and alcohol consumed. The reaction is controlled to give complete conversion of ethylene oxide. The contact time has been calculated on the assumption that the reactor capacity is 3.5 cubic m. Either acids or bases may be used as catalysts in the reaction between ethylene oxide and alcohol. However, acids are corrosive and must be neutralized before treating the crude reaction product, and alkalies lead to the formation of resins with the acetaldehyde present in the ethylene oxide. Because of the above reasons a noncatalytic process was developed. The Germans also developed a process using aqueous ethyl alcohol, but as this involves a difficult products separation, it is not preferred.

27 2.6.2

Second Process Production of glycol monobutyl ether by reaction of formaldehyde is an n-butanol with carbon monoxide and hydrogen in the presence of catalyst system. In this production of glycol butyl ether are prepared by reaction of an aldehyde, a monohydric alcohol and synthesis gas in the presence of the catalyst. The processes are as follow:

Reaction 1

Reaction 2 Figure 2.7: Reaction for Second Process A wide variety of alcohol and aldehydes may also be employed in the process instead of n-butanol and formaldehydes. This process provide high degree of selectivity by yields of ethylene glycol butyl ether and ethyelene dibutyl ether as high as 64 percent based on the formaldehyde charged to the reactor have been obtained. Pressure reactor was charged in this process for mixture of catalyst, formaldehyde in n-butanol. After flushing with nitrogen, the reactor then was sealed and flushed a with a gaseous mixture containing equal molar amounts of carbon monoxide and hydrogen following which it was pressured range 1000 psi to 5000 psi with. This pressure represents the total pressure generated by all the reactants although they are substantially due to the carbon monoxide and hydrogen fraction. The relative amounts of carbon monoxide and hydrogen which may initially present in the syngas mixture are variable and these amounts can be varied over the wide range. The mole ration of CO: H2 range from 20:1 up to about 1:20 but preferably from 5: 1 to 1:5. The mixture then finally heated about 1600C with agitation. The range operability can be varied from about 500C to about 3000C when super atmospheric syngas are employed. A narrower range of operability temperature preferred was about 1000C to about 2500C. After 4 hours reaction, the reactor was allowed to cool and the excess gaseous vented while the deep brown liquid product was recovered. The desired product then can be recovered by conventional distillation process. The unreacted n-butanol and catalyst can be recycled to improve the process yield. By product found such as water and some dibutoxymethane .

28 2.6.3

Third Process

By contacting

a glycol

with a monohydric alcohol in

the

presence of

a

polyperfluorosulfonic acid resin catalyst under conditions is effective to produce the glymes. This method can be used to produce monoglyme , ethyl glyme, diglyme, ethyl diglyme,triglyme, butyl diglyme, tetraglyme and producing 1,4-dioxane, water as by product.

Figure 2.8: Reaction for Third Process

A feed solution consisting of 3 moles ethylene glycol, 12 moles n-butanol and about 0.0015 of NAFION 1100 EW Polymer (H+ form) were charged to the autoclave reactor (high pressure reactor). After sealing and pressure testing, all the mixture were agitated at 1900 rpm and pressurized to 700 psi to 1000 psi with nitrogen due to high vapour pressure of the reactants and the products formed during the reaction. Along the reaction process, the autoclave was depressurized and being repeated 2 or 3 times to ensure complete deoxygenation. As continuous process, a recycle feed nominally by weight of 2.4% of NAFION 1100 EW Polymer (H+ form), 12.7% ethylene glycol monobutyl ether, 20.7% ethylene glycol and 64.2% n- butanol was continuously added to the reactor. As for using high preesure pump, the feed solution was added at rate equivalent to 0.2 of the reactor working volume per hour. into the autoclave mixture An elevated reaction temperature allows the catalyst to partially dissolve in the reaction mixture, thus it provides semi homogeneous catalyst condition. Production of the glymes occurs at the reaction temperature in range of 1000C to 3000C but in this case preferably 1600C to 2200C to kept the mixture 2000C. For the monoglymes and diglymes selected operation temperature is 1900C to 2100C and about 4 to 5 hours reaction.

29 Once the reaction has been completed, the reactor contents are cooled to ambient temperatures and the reactor contents are separated by conventional distillation column and the 1,4- dioxane is formed as co-product while the water and the dialkyl ether produces as by product. As for result found about 75.7% of the ethylene glycol was converted in the reaction with 71.4% of yield and with 94.3% selectivity.

30 2.6.4

Justification of Process Selection

Table 2.5: Comparison of the Process Criteria Factor

Weight

Score Index

Total Score

(%)

P1

P2

P3 80

P1 0.13 x 65 = 8.45

P2 0.13 x 85 = 11.05

P3 0.13 x 80 = 10.4

Raw material (Price, Supplier)

13

65

85

Product Selectivity

13

72

65

94

9.36

8.45

12.2

Product Yield

13

85

61

72

11.05

7.93

9.36

Reactant Conversion

8

99

90

75

7.92

7.2

6

Safety Factor

12

80

70

75

9.6

8.4

9

Environment Study

8

80

65

70

6.4

5.2

5.6

By Product

5

85

65

65

4.25

3.25

3.25

Operating Condition

3

85

65

80

2.55

1.95

2.4

Energy Involve

5

85

65

80

4.25

3.25

4

Maintenance

4

85

85

85

3.4

3.4

3.4

Catalyst

4

80

80

80

3.2

3.2

3.2

Separation / Purification

7

80

75

75

5.6

5.25

5.25

Reaction

5

90

70

70

4.5

3.5

3.5

80.53

66.83

77.56

Total Credit

100

31

2.6.4.1 Raw Material The basic raw material for all three processes is n-butanol. Hence the comparison on the price only can be made on the other raw material required. For the process 1 (P1), ethylene oxide is the other raw material which have a prices about £850 per ton worldwide. While for the Process 2 (P2) using ethylene glycol £550 and for the process 3 (P3) carbon monoxide, hydrogen and formaldehyde which have total price more affordable which more cheap to operate for a long time process. So, P3 provide better advantage in term of pricing. For the supplier of the raw material, all three processes categorized almost the same as the supplier in around Malaysia itself. 2.6.4.2 Product Selectivity & Yield Table 2.6: Process 1 Composition effluent wt% Process EO P1

0.2

Conversion Selectivity

Yield

BuOH

EGBE

DEGEBE

TEGBE

%

%

%

57.5

30.5

9.8

22

99

72

85

Table 2.7: Process 2 Composition effluent wt%

Conversion Selectivity

Yield

Process

H20

BuOH

EGBE

EGDBE

BuOCH

%

%

%

P2

4.5

75.2

17.8

2

0.5

90

65

61

Table 2.8: Process 3 Composition effluent wt%

Conversion Selectivity

Yield

Process

EG

BuOH

EGBE

EGDBE

%

%

%

P2

0.5

68.5

24

7

75

94

72

32 Base on the product yield and selectivity clear enough that route process 1 indicate higher yield and conversion by 85% and 99% respectively. But the P3 gave higher selectivity up to 94%. Hence, the P1 have advantages in term of the product specification or condition when operating.

2.6.4.3 Safety Factor Safety process is very looking forward nowadays in chemical plant. It is important to ensure the hazard of the process can be avoided as much as can be done. In order to accomplish the mission the best route lead to safe operation and environment must be take an account. As for all the three process available, all have advantages and disadvantages itself but the P2 provide more safe raw material to be handle 2.6.4.4 Environment Study The effluent is must to treat first before the waste is discharge at final discharge point. The P1 shows the last product with higher ethers needs to be treating because it consider as waste. P1 and P3 environmentally are better compare than the P2 in term of the air pollution. P2 is release more CO2 during the process. 2.6.4.5 Reactant Conversion & by-Product As mentioned in the product evaluation, the reactant conversion is another important thing to be considered to ensure full conversion occurs during the process. P1 indicated higher reactant conversion compared than others. For the by- product criteria, P1 produces about another 2-3 other higher ether which are di, tri and tetra ethylene glycol butyl ether. And all of this by-product have their own market demand and suitable to be sell in the world market. P2 and P3 on the other hand, produced only 1 by-product. In term of the profitability study, P1 route are most preferable for a long term process.

33 2.6.4.6 Operating Condition & Energy Consumption i.

P1 operating conditions are about 2000C and at 25-45 atm,

ii.

P2 operating conditions are about 100 – 2500C and at almost 100 atm

iii.

P3 operating conditions are about 2000C and at 70 atm.

As comparisons, the P2 conditions are needs more energy to operate compare to other 2 process because the reaction for P2 requires high pressure and temperature. The amount of energy must be consistent to handle and control the process.

2.6.4.7 Maintenance Since all the three processes are in continuous process, the maintenance is almost the same as comparison. The continuous process seems more complicated in term of maintenance over that batch process. 2.6.4.8 Separation and Purification Separation and purification is another heavy important thing to be considered in processing plant. Higher purity during reaction is important to ensure the energy consumption during the purification can be reduced. As can be seen roughly, the P1 indicated higher yield product with a good conversion which lead to easy purification compared to the others route. Other than that, the catalyst separation also needs to be emphasized. The heterogeneous catalysts are considered better separation instead of homogeneous catalyst. 2.6.4.9 Catalyst All the three process represent different catalyst requirement to enhance the process. All three processes P1, P2 and P3 provide heterogeneous catalyst by fix type of catalyst use for the process. In the production of EGBE, heterogeneous seems has advantages due to the further separation whereby easy to be done. Homogeneous base catalyst may have drawback that adduct having at least 2 mole of olefin oxide added. It is also generally difficult to remove the homogeneous catalyst from the system purification processes and automatically resultant toxicity to the product or waste. Besides, it difficult controls the positioned selectivity of reaction.

34

2.6.5

Catalyst Selection

Since the Process 1 is become the main route selected for this production of EGBE. The catalyst is important to determine since the catalyst involve are heterogeneous. Three type of catalyst which is Zeolite, Anion Exchnage Resin and Leyered Double Hydroxide (LDH) for this process must be analyzing in order to optimize the processto be high catalyst activity, procudtivity, and selectivity but low in term of cost.

2.6.5.1 Zeolite Catalyst One of the widely use inorganic materials for the catalytic activity are cationic clays. These clays comprise negatively charge metal silicate clays. For this process, the catalyst present is a metallosillicate catalyst. The metellosilicate use has generic composition which relative mole ratios of various oxides. The sodium exchange USY zeolite (Si/Al =80) which is the crystalline metallosilicate used are weakened acidity and basic in character. However, it is necessary to replace sufficient number of hydrogen inos present in metallosilicate with alkali metal ions for resultant is basic in character. This catalyst used suitability for a large pore type.

The preparation of the catalyst to be activate is by heating it in air flow at elevated temperature from 2500C – 6500C for about 5- 30 hours before can be use. The operating temperature for the catalyst to operate in optimize condition are form ambient up to 3500C at 50 bar. A particular advantage of the zeolite catalysts is that they are regenerable and can be used for several cycles. Besides, the lifetime of the zeolite catalyst will up to 2 years. Table 2.9: Zeolite Catalyst Selectivity of product % w/w

Conversion EO

byproduct

Catalyst

EGBE

Higher ethers

%

% w/w

Zeolite

92.8

4.9

40

2.3

35 2.6.5.2 Anion Exchange Resin Catalyst Solid base catalyst that comprises as the substrate a polymer vinyl aromatic compound which has a structure a quaternary ammonium group is bonded to aromatic group via a linking group having chain length of at least 3. The advantages is that having certain specific structure as the catalyst with a good performance respect to durability and consequently will produce terminal adduct type structure high reactivity and selectivity. This type of catalyst provide low price and better lifetime which about 3-5 years and can be regenerate several cycle. The operating temperature for the catalyst is about 50 0C to 2000C. The regeneration process can be simple as by shifting the equilibrium to the left. And it can be accomplished by increasing concentration of X-. Table 2.10: Anion Exchange Resin Catalyst Selectivity of product % w/w

Conversion EO

byproduct

Catalyst

EGBE

Higher ethers

%

% w/w

AER

80

19.8

99

0.2

36 2.6.5.3 Layered Double Hydroxide (LDH) Catalyst LDH comprises layer double hydroxide clay with its layered structure intact and having interlamellar anions at least some of which are metal ions. LDH is type of anion clays which intercalated metal oxides or hydroxide. On the performance part, LDH clays contain mainly carbonate which normally has low activity as catalyst for the preparation of glycol ethers. The operating temperature for the catalyst to operate in optimize condition are form ambient up to 2500C at 50 bar. The lifetime more less same as zeolite catalyst even the regeneration process also similar to the zeolite catalyst procedure but the catalyst easily recovered post reaction and could be recycled with no loss in selectivity.

Table 2.11: Catalyst for the Preparation of Glycol Ether Selectivity of product % w/w

Conversion EO

byproduct

Catalyst

EGBE

Higher ethers

%

% w/w

LDH

95

5

80

0.3

37 2.6.5.4 Justification on Catalyst Selection Stage

Table 2.12: Catalyst Selection Stage

Criteria Factor

Weight

Score Index

Total Score

70

Zeolite 0.25 x 65 = 16.25

AER 0.25 x 85 = 21.25

LDH 0.25 x 70 = 17.5

75

85

15

18.75

21.25

75

80

75

15

16

15

15

75

80

85

11.25

12

12.75

Separation Process

15

80

80

85

12

12

12.75

Total Credit

100

69.5

80

79.25

(%)

Zeolite

AER

LDH

Price, Operating Cost

25

65

85

Performance

25

60

Lifetime

20

Regeneration process

38 2.6.5.5 PFD of the Selected Process

39 CHAPTER 3

MARKET ANALYSIS

3.1 INTRODUCTION Market analysis can be defined as a survey of the demand and supply of a particular product including main product and by- product that an industry intends to produce for sale locally, regionally or globally. It is important to determine the profitability of a product in the market. Besides that, it will enable a company to determine related parties such as competitors, suppliers and buyers of the product.

The largest volume of Glycol produced in the market is Ethylene Glycol because of its wide variety of applications and uses. Other Glycols include Butyl Cellusolve, Butyl Glycol, Butyl Oxitol, Ethylene Glycol Monobutyl Ether, 2-butoxyethanol, and Ethanol 2butoxy.

Glycol products can be used as solvents or plasticizer for plastic and varnish, dehydrating and textile conditioning agents, general purpose cleaners, water-based coating and paint and also preservatives. Because of their chemical and physical properties, Glycol that having a high boiling point is used as liquid desiccant for the dehydration of natural gas . Specifically, this section is all about the market and the production of Butyl Glycol Ether as well as the raw materials (Ethylene Oxide and n- Butanol) where by Ethylene Glycol Butyl Ether (Butyl Cellosolve) is taken as the main product while Diethylene Glycol Butyl Ether (Butyl CARBITOLTM), Triethylene Glycol Butyl Ether (Butoxytriglycol) and Tetraethylene Glycol Butyl Ether (Butoxytetraglycol) as the byproducts.

Furthermore, this section will include the break-even analysis which is the analysis of income, cost and profit structures with particular reference to the break-even point. The break-even point is that level of sales at which neither profit nor loss is made,

40 it is the lowest point at which fixed costs are fully recovered.

All information and

dataquoted in this market analysis were sourced from various websites in the internet, other journals, World Trade Atlas and Department of Statistics Malaysia. 3.2 SUPPLY AND DEMAND OF BUTYL GLYCOL ETHER 3.2.1

World’s Demand and Supply of Butyl Glycol Ether Table 3.1: World demand of Butyl Glycol Ether Year

Demand (Tonnes metric / year)

1972

58500

1975

58500

1983

103500

1984

121950

1986

135000

1995 (Source: World Chemical Report, 1996)

183800

41

Tonnes Metric

WORLD DEMAND OF BUTYL GLYCOL ETHER 200000 180000 160000 140000 120000 100000 80000 60000 40000 20000 0 1972

1975

1983

1984

1986

1995

Years Figure 3.1: The trend line for world demand of Butyl Glycol Ether from 1972 – 1995 (Source: World Chemical Report, 1996)

The business in these solvent is changing around the world and more changes are expected. Therefore Butyl Glycol Ether market has being rapidly growth, especially in the regions of economic development. Figure 3.1 above illustrated a graph with an approximately 58500 tonnes metric per year of Butyl Glycol Ether were produced in the United States in the 1970s. However, there was a significant overall increase in production during the early eighties which was reported to be more than 103500 tonnes metric per year. Production of Butyl Glycol Ether reached 121950 tonnes metric year in 1984 and increased to over 135000 tonnes metric per year in 1986. A production volume of 183800 tonnes metric year of Butyl Glycol Ether has been estimated for 1995. It is predicted that the pattern will continue for further years because demand of the Butyl Glycol Ether in the world are predicted increasing about 30%.

Major producers of Butyl Glycol Ether in United States are Dow Chemical, (Midland Michigan), Eastman Chemical Co., Texas Eastman Co. Division (Longview, Texas), Occidental Petroleum Corporation, Oxy Petrochemicals, Inc. (Dallas, Texas), Shell Chemical Co. (Geismar, Lousiana) and Union Carbide Corporation, Solvents and Intermediates (Seadrift, Texas).

42

Table 3.2: World solvent-based coatings demand by region (tonnes metric) Region Year

2000

2005

2010

North America

13580

13550

13325

Western Europe

12950

12930

12845

Japan

11452

11587

11715

Other Asia-Pacific

13681

14774

20580

Rest of World

13470

14229

15095

(Source: Dow Chemical Company)

World solvent-based coatings demand by region 24000

Tonnes Metric

22000 20000 North America 18000

Western Europe Japan

16000

Other Asia-Pacific Rest of World

14000 12000 10000 2000

2005

2010

Figure 3.2: World solvent-based coatings demand by region (tonnes metric) (Source: Dow Chemical Company) From Table 3.2 and Figure 3.2 above, it is predicted that uses of Butyl Glycol Ether in paints and coatings for both North America and Western Europe will decline by over 8% and 4% respectively between year 2000 and 2010. However it will increase by over 18% in Japan, more than 66% in other Asia Pacific countries and 47% for the rest of the world. Furthermore, the global demand for Butyl Glycol Ether is projected to

43 increase in the future mainly due to higher demands from Asia, which is the target region demand for our product. The United States and Western Europe are the major producers. However, the use of this product as solvents for paints is decreasing in the developed world because of environmental concerns.

Since, United States and Western Europe regions slowly to stop produce the Butyl Glycol Ether because of environment concerns; it will give high opportunity to the Asia Pacific region to become the main producer and supplier of the Butyl Glycol Ether. Furthermore, Asia Pacific regions are the main demander of Butyl Glycol Ether in the solvent- based coatings industries. From Figure 3.3 below, it is showed that the demands of the Butyl Glycol Ether are higher than the supply in Asia Pacific regions from year 2008 to 2010. This pattern will continue for further years because demand of the Butyl Glycol Ether are predicted increasing about 30%.

Asia Demand and Supply of Butyl Glycol Ether 40000 35000 Tonnes Metric

30000 25000 20000

Demand

15000

Supply

10000 5000 0 2008

2009

2010

2011

2012

2013

Figure 3.3: Asia demand and supply of Butyl Glycol Ether from 2008 to 2013 (Source: Dow Chemical Company & MATRADE) Since, the supply are increasing too but it is not sufficient to fulfill the market demand because of United States and Western Europe regions are slowly to stop produce the Butyl Glycol Ether because of environment concerns.

44 As the conclusion, the production of 100,000 tonnes of Butyl Glycol Ether can be profitable because of the potential high demand particularly in Asia especially in Asia Pacific regions. 3.2.2

Malaysia’s Demand and Supply of Butyl Glycol Ether

The OPTIMAL group of companies (OPTIMAL) is one of the largest company that involve in producing chemical compounds from petroleum derivatives. Established in July 1998, OPTIMAL comprises three companies which are OPTIMAL Olefins (Malaysia) SDN BHD, OPTIMAL Glycols (Malaysia) SDN BHD and OPTIMAL Chemicals (Malaysia) SDN BHD. OPTIMAL manufactures more than 75 products that are supplied to its customers locally and exported to the Asia Pacific markets. Therefore, OPTIMAL Chemical (Malaysia) Sdn Bhd produces and exports Butyl Glycol Ether to various countries across Asia. Based in Kerteh, Terengganu, OPTIMAL Company is the one of largest producer of exports Butyl Glycol Ether in a single location, producing 60000 tonnes metric per year. OPTIMAL's key markets include South East Asia, Japan, South Korea, China and Taiwan. About 60 percent of the Group's products are utilized to meet local demands with the remaining 40 percent for the export market. According to the World Chemical Report, 2010, the price of Butyl Glycol Ether increased from RM 15.83 per kg or per 0.001 tonnes metric in October 2009 to RM 16.52 per kg or per 0.001 tonnes metric in April 2010. Refer to the Table 3 below, it illustrated that the export of Butyl Glycol Ether by other country from the Malaysia was increase from year 2008 to 2010. It was proved that Malaysia is the one of the successful producer of Butyl Glycol Ether in the world and has a good opportunity in the market global to become a major producer in Asia and world. While in Table 4 below showed that the Malaysia was slowly to stop to export of Butyl Glycol Ether from other country because Malaysia believe that it can become the producer of Butyl Glycol Ether and depend all into their own productions. Table 3.3: The Malaysia‟s export of Butyl Glycol Ether by country 2008 Country

2009

2010

Value (RM /

Millions

Value (RM /

Millions

Value (RM /

Millions

kg)

Kg

kg)

Kg

kg)

Kg

45 China

15.23

5.540

12.98

10.84

14.30

11.89

Indonesia

15.40

1.691

13.11

0.9592

14.30

1.858

Japan

14.92

1.482

13.47

0.3764

14.31

1.185

Thailand

15.24

0.7889

13.02

2.264

14.26

1.130

Philippines

14.75

1.377

12.47

1.196

14.12

1.116

Taiwan

15.02

1.136

12.96

2.103

14.24

0.7845

Singapore

16.03

0.1756

13.76

0.4127

15.21

0.7166

Vietnam

16.48

0.2666

14.22

0.5518

15.12

0.3064

Australia

15.20

0.6518

12.83

1.121

13.86

0.3064

India

-

-

13.49

0.2889

15.04

0.09216

New

14.99

0.3024

12.98

0.06218

14.29

0.06133

Sri Lanka

-

-

14.29

0.09000

14.70

0.05040

South Korea

-

-

12.82

0.6520

14.14

0.01150

Brunei

-

-

-

-

16.45

0.02160

Zealand

Darussalam Source: MATRADE, April 2010

Table 3.4: The Malaysia‟s import of Butyl Glycol Ether by country 2008 Country

2009

2010

Value (RM /

Millions

Value (RM /

Millions

Value (RM /

Millions

kg)

Kg

kg)

Kg

kg)

Kg

20.94

0.2713

14.89

0.3535

15.35

0.1269

India

15.29

0.0156

14.79

0.6670

15.30

0.09204

Taiwan

18.03

0.1704

15.01

0.02302

14.85

0.1010

United

113.96

0.02811

21.54

0.02385

18.69

0.04254

Singapore

11.82

0.01138

13.03

0.03865

11.59

0.02598

Germany

30.06

0.02876

14.17

0.1000

15.65

0.0060

United Arab

18.55

0.0250

-

-

-

-

United States

Kingdom

Emirates

46 Brazil

15.37

0.01255

-

-

-

-

China

50.18

0.00260

-

-

-

-

France

17.17

0.08134

14.35

0.03781

-

-

Japan

45.75

0.0006

-

-

-

-

South Korea

-

-

25.29

0.00882

-

-

Netherlands

20.23

0.04588

-

-

-

-

Panama

20.39

0.01093

-

-

-

-

Source: MATRADE, April 2010

3.3

AN OVERVIEW ON RAW MATERIALS

The production of Butyl Glycol Ether is dependent on raw materials which are Butyl Alcohol (n- Butanol) and Olefin Oxide (Ethylene Oxide) as the excess reagent and limiting reactant respectively. The reaction between Ethylene Oxide and n- Butanol in the presence of Anion Exchange Resin as a catalyst will result in the production of Butyl Glycol Ether.

3.3.1

SUPPLY AND DEMAND OF ETHYLENE OXIDE

3.3.1.1 World’s Demand and Supply of Ethylene Oxide

Table 3.5: World Demand and Price of Ethylene Oxide

Year

Demand

Price (RM / 0.001 tonnes

(Tonnes metric / year)

metric)

1996

357000

4.39

1997

360000

4.39

1998

364000

4.39

47

1999

371000

4.90

2000

377000

4.90

2001

404000

4.90

2002

-

-

2003

-

-

2004

-

5.41

2005

-

5.83

2006

-

-

2007

-

-

2008

649000

6.34

2009

759000

6.42

2010

706000

6.62

(Source: World Chemical Report, 2005 and MATRADE, May 2010)

48

WORLD DEMAND OF ETHYLENE OXIDE 410000

Tonnes Metric

400000 390000 380000 370000 360000 350000 340000 330000 1996

1997

1998

1999

2000

2001

Year Figure 3.4: The trend line for world demand of Ethylene Oxide from 1996 – 2001 (Source: World Chemical Report, 2005)

RM / 0.001 tonnes metric

WORLD PRICE OF ETHYLENE OXIDE 5 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 1996

1997

1998

1999

2000

2001

Years Figure 3.5: The trend line for world price of Ethylene Oxide from 1996 – 2001 (Source: World Chemical Report, 2005) Figure 3.4 above illustrated a graph with a gradual increase of demand on Ethylene Oxide from 357000 tonnes metric per year in 1996 to 404000 tonnes metric per year in 2001. The increasing demand is the highest in year 2000 to year 2001 which is 7% compared to the other years which is only increased by 1%. The demand of

49 Ethylene Oxide is continually increasing in year 2008 to 2010 which are from 649000 to 706000 tonnes metric per year respectively.

Furthermore, the price per 0.001 tonnes metric remains stable at around RM 4.39 from year 1996 to 1998. The price increased to RM 4.90 per tonnes metric started from year 1999 and remains the same up to year 2001(World Chemical Report, 2005). The price of Ethylene Oxide in year 2004 per 0.001 tonnes metric is RM 5.41 and increased to RM 5.83 per 0.001 tonnes metric in year 2005 (Dow Chemical Company). Based on the demand of Ethylene Oxide from year 1996 to 2001, it is predicted that this trend of the price will continue and keep increasing until year 2010 or 2011. The assumption was proved by the increasing of Ethylene Oxide‟s price in year 2008 to 2010 which are RM 6.34, RM 6.42 and RM 6.62 per 0.001 tonnes metric respectively (World Chemical Report, 2005 and MATRADE, May 2010).

Producer of Ethylene Oxide 700000 600000 500000 400000 300000 200000 100000 0 BASF, Geismar, Los Angeles

Production (Tonnes Metric / year) 204000

Dow, Seadrift, Texas

410000

Dow, Taft, Texas

667000

Dow, Plaquemine, Los Angeles

279000

Eastman, Longview, Texas

104000

Equistar, Bayport, Texas

338000

Formosa, Point Comfort, Texas

248000

Huntsman, Port Neches, Texas

510000

Old World Industries, Clear Lake, Texas

315000

Figure 3.6: Producer of Ethylene Oxide in the United States in 2006 (Source: World Chemical Report, 2005)

50 Since the United States is the major producer of Ethylene Oxide in the world, according to the Figure 3.6 above lists the major producers of Ethylene Oxide in the United States in year 2006. The Dow Chemicals accounted for more than 50% of the producer (World Chemical Report, 2005). One of the producers of Ethylene oxide in Asia is Singapore which is located at Jurong Island (Merbau). Ethylene Glycols (Singapore) Pte Ltd (EGS) is one of the companies operating as part of the petrochemicals complex on Jurong Island, Singapore. 3.3.1.2 Malaysia’s Demand and Supply of Ethylene Oxide Optimal (Chemicals) Sdn.Bhd. in Kerteh, Terengganu is the one of the company in Malaysia which produces Ethylene Oxide with an annual production of 385000 tonnes metric. The Ethylene Oxide which produces by this company is consumed locally and exported to the Asia Pacific markets. Other than that, this company also produces Ethylene, Ethylene Glycol and Ethoxylates with an annual production of 600000, 360000, and 85000 tonnes metric respectively. (Source: Chemicals- Technology.com. OPTIMAL's key markets include South East Asia, Japan, South Korea, China and Taiwan. About 60 percent of the products are utilized to meet local demands with the remaining 40 percent for the export market.

Table 3.6: The specification of Ethylene Oxide plant in Kerteh Key Data Order year

2001

Plant type

Integrated Petrochemicals site

Location

Kerteh

Estimated investment

$300 million

Completion

2001

Key Players Sponsor

Petronas, Union Carbide

Lead Contractor

Linde AG

Output chemicals

Tonnes per year

Ethylene

600,000

Ethylene Glycol

360,000

Ethylene Oxide

385,000

51 Ethoxylates (TRITON and TERGITOL surfactant,

85,000

CARBOWAX polyethylene glycols and UCON polyalkylene glycols) Isobutanol

140,000

Isobutanol Derivatives (isobutyl acetate, and

160,000

isobutyl acrylate Ethanolamines

75,000

UCARSOL gas-treating solvents

10,000

(Source: Chemicals- Technology.com)

3.3.2

SUPPLY AND DEMAND OF N- BUTANOL

3.3.2.1 World’s Demand and Supply of n- Butanol

Table 3.7: World demand and price of n- Butanol

Year

Demand

Price (RM / Kg)

(Tonnes metric / year)

1996

650000

4.22

1997

695000

4.22

1998

740000

4.22

1999

790000

4.22

2000

792000

4.64

52

2001

810000

4.64

2002

-

-

2003

-

-

2004

-

5.40

2005

-

7.94

2006

-

-

2007

-

-

2008

850000

8.50

2009

890000

8.70

2010

900000

9.00

(Source: World Chemical Report, 2005, Dow Chemical Company and MATRADE, Apr 2010)

53

WORLD DEMAND OF N- BUTANOL

Tonnes Metric

850000 800000 750000 700000 650000 600000 1996

1997

1998

1999

2000

2001

Year Figure 3.7: The trend line for world demand of n- Butanol from 1996 – 2001 (Source: World Chemical Report, 2005 & Dow Chemical Company)

WORLD PRICE OF N-- BUTANOL RM / Tonnes metric

4.7 4.6 4.5 4.4 4.3 4.2 4.1 4 1996

1997

1998

1999

2000

2001

Years Figure 3.8: The trend line for world price of n- Butanol from 1996 – 2001 (Source: World Chemical Report, 2005 & Dow Chemical Company)

Figure 3.7 above illustrated a graph with a gradual increase of demand on nButanol from 650000 tonnes metric per year at RM 4.22 per 0.001 tonnes metric in 1996 to 810000 tonnes metric per year at RM 4.64 per 0.001 tonnes metric in 2001. This

54 reflected a 25% increase in the demand with only a corresponding increase of 10% in the price per kg (Table 3.7). The price per kg or per 0.001 tonnes metric remains static at RM 4.22 from year 1996 to 1999 despite an increase in demand by 20% from 650000 to 760000 tonnes metric per year. The price increased to RM 4.64 per 0.001 tonnes metric started from year 2000 and remains constant in year 2001 (World Chemical Report, 2005).

In year 2004, the price of n- Butanol is RM 5.40 per 0.001 tonnes metric and started to increase to RM 7.94 per 0.001 tonnes metric in year 2005. (Source: Dow Chemical Company). Based on the demand and prices of n- Butanol from year 1996 to 2005, it is predicted that the price and demand of n- Butanol will keep increasing until year 2010 or 2011. The assumption was proved by the increasing of n- Butanol‟s price in year 2008 to 2010 which are RM 8.50, RM 8.70 and RM 9.00 per 0.001 tonnes metric respectively (World Chemical Report, 2005 and MATRADE, Apr 2010). Table 3.8: Producer of n- Butanol in 2008 Country

Production (Tonnes metric / year)

United States

1295000

Western Europe

1068000

China

881000

(Source: Dow Chemical Company)

Table 3.8 above shows the world producer of n- Butanol. The world production of n- Butanol is 3237000 tonnes metric per year. It is mainly focused in the United States, Western Europe and China, which account for 40%, 33% and 9% respectively of the world‟s total. The United States is the largest n- Butanol producer in the world.

55

Producer of n- Butanol

300000 250000 200000 150000 100000 50000 0

BASF, Freeport, Texas

Production (Tonnes metric / year) 207000

Celanese, Bay City, Texas

223000

Dow, Taft, Los Angeles

270000

Dow, Texas City, Texas

262000

Eastman, Longview, Texas

131000

Figure 3.9: Producer of n- Butanol in the United States in 2008 (Source: World Chemical Report, 2009)

Figure 3.9 above shows the current major producers of n- Butanol in the United States in year 2008 since United States is the major producer of the n- Butanol. Dow Chemicals in Los Angeles and Texas together produced nearly 50% of the total nButanol (World Chemical Report, 2009). In Asia, China is the major n- Butanol producer with an annual production of 881000 tonnes metric. The companies that produce n- Butanol are BASF-YPC Company Ltd Beijing Dongfang, Petrochemical Co. CNPC Jilin, Petrochemical Co. PetroChina Daqing, Petorchemical Co. Ltd Sinopec Qilu and Petrochemical Corp. (China Chemical Reporter, 2007) 3.3.2.2 Malaysia’s Demand and Supply of n- Butanol Optimal Chemicals Sdn.Bhd. in Kerteh, Terengganu is the only company in Malaysia which produces n- Butanol with an annual production of 140000 tonnes metric. The nButanol which produces by this company is consumed locally and exported to the Asia

56 Pacific markets (Chemicals- Technology.com). OPTIMAL's key markets include South East Asia, Japan, South Korea, China and Taiwan. About 60 percent of the products are utilized to meet local demands with the remaining 40 percent for the export market.

Table 3.9: The specification of Ethylene Oxide plant in Kerteh Key Data Order year

2001

Plant type

Integrated Petrochemicals site

Location

Kerteh

Estimated investment

$300 million

Completion

2001

Key Players Sponsor

Petronas, Union Carbide

Lead Contractor

Linde AG

Output chemicals

Tonnes per year

Ethylene

600,000

Ethylene Glycol

360,000

Ethylene Oxide

385,000

Ethoxylates (TRITON and TERGITOL surfactant,

85,000

CARBOWAX polyethylene glycols and UCON polyalkylene glycols) n- Butanol

140,000

Isobutanol Derivatives (isobutyl acetate, and

160,000

isobutyl acrylate Ethanolamines

75,000

UCARSOL gas-treating solvents

10,000

(Source: Chemicals- Technology.com)

57 3.4

CONCLUSION

The price per kg of the raw materials for Ethylene Oxide is the remains stable at around RM 4.39 per 0.001 tonnes metric from year 1996 to 1998. The price increased to RM 4.90 per 0.001 tonnes metric started from year 1999 and remains the same up to year 2001 (World Chemical Report, 2005). The price of Ethylene Oxide in year 2004 per 0.001 tonnes metric is RM 5.41 and increased to RM 5.83 per 0.001 tonnes metric in year 2005 (Dow Chemical Company). Based on the demand of Ethylene Oxide from year 1996 to 2001, it is predicted that this trend of the price will continue and keep increasing until year 2010 or 2011. The assumption was proved by the increasing of Ethylene Oxide‟s price in year 2008 to 2010 which are RM 6.34, RM 6.42 and RM 6.62 per 0.001 tonnes metric respectively (World Chemical Report, 2005 and MATRADE, May 2010). Whereas, the price of n- Butanol is RM 5.40 per 0.001 tonnes metric and started to increase to RM 7.94 per 0.001 tonnes metric in year 2005. (Dow Chemical Company). Based on the demand and prices of n- Butanol from year 1996 to 2005, it is predicted that the price and demand of n- Butanol will keep increasing until year 2010 or 2011. The assumption was proved by the increasing of n- Butanol‟s price in year 2008 to 2010 which are RM 8.50, RM 8.70 and RM 9.00 per 0.001 tonnes metric respectively. (World Chemical Report, 2005 and MATRADE, May 2010).

For the both raw materials, Optimal Chemicals Sdn.Bhd. in Kerteh, Terengganu is the only company in Malaysia which produces Ethylene Oxide and n- Butanol with an annual production of 385000 and 140000 tonnes metric respectively.

For the product, the price of Butyl Glycol Ether increased from RM 15.83 per 0.001 tonnes metric in October 2009 to RM 16.52 per 0.001 tonnes metric in April 2010. The global demand for Butyl Glycol Ether is projected to increase in the future mainly due to higher demands from Asia, which is the target region demand for our product. The United States and Western Europe are the major producers. However, the use of this product as solvents for paints is decreasing in the developed world because of environmental concerns.

The production of 100,000 tonnes of Butyl Glycol Ether can be profitable because of the potential high demand particularly in Asia. Because of that, the export of

58 Butyl Glycol Ether by other country from the Malaysia was increase from year 2008 to 2010 especially from Asia region country. It was proved that Malaysia is the one of the successful producer of Butyl Glycol Ether in the world and has a good opportunity in the market global to become a major producer in Asia and world. Furthermore, Malaysia was slowly to stop to export of Butyl Glycol Ether from other country because Malaysia believe that it can become the producer of Butyl Glycol Ether and depend all into their own productions. 3.5

BREAK EVEN ANALYSIS

3.5.1

Introduction

Break even analysis is a technique used to analyze income, cost and profit structures with particular references to the break even point which is the point at which the product stops costing money to produce and sell, and starts to generate a profit for company. In order for that purpose, the break even analysis requires an estimation of fixed costs, variable cost and total revenues.

3.5.2

Total Cost

According to Coulson and Richardson‟s (2001), total cost is also known as a operating costs and can be divided into two groups which are fixed cost and variable cost. 3.5.2.1 Fixed Cost (FC) Fixed costs are the costs that do not vary with production rate. These are the type of bills that have to be paid whatever the quantity produced in the process production. It includes; 1) Maintenance (labor and materials) 2) Operating labor 3) Laboratory cost 4) Supervision 5) Plant overheads 6) Capital charges

59 7) Rates (and any other local taxes and tariff) 8) Insurance 9) License fees and royalty payments 10) Administrative and management cost Fixed cost can be calculated by using this equation: FC = QT x f

(3.1)

where; QT = total plant capacity per year and f = fixed cost per tone

3.5.2.2 Variable Cost (VC) Variable costs are the costs that are dependent on the amount of product produced in the process production. It includes; 1) Raw materials 2) Miscellaneous operating materials 3) Utilities 4) Shipping and packaging Variable cost can be calculated by using this equation: VC = V x Q

(3.2)

where; V = Variable cost per tone Q = Capacity Total cost can be calculated by using this equation: TC = FC + VC

(3.3)

where; FC = Fixed cost VC = Variable cost 3.5.3

Total Revenue

Total revenue is the total amount of money generated from the sale of output. It can be calculated by using this equation:

60 TR = PQ

(3.4)

where; P = Price per unit Butyl Glycol Ether Q = Quantity (tonnes) 3.5.4

Break Even Point

The objective of the break even analysis is to determine the quantity at which the product at a price will generate enough revenue to start earning a profit. The break even point is to estimate and illustrated the volume or capacity for the company to reach the total cost equal to the total revenue and no profit was earned yet. So, it can conclude that; Total Revenue = Total Cost

(3.5)

TR = TC According to Coulson and Richardson‟s (2001), the breakeven point QBE is determined by using relations for revenue and cost at different values of the variable, Q. The Q may be expressed in units per year, percentage of capacity, hour per month, etc. For example, at some value of variable the revenue and the total cost relations will intersect to identify the break even point, QBE. If Q > QBE, there is a predictable profit. But if Q < QBE, there is a loss. Profit is defined as; Profit = Total Revenue - Total Cost

(3.6)

Break even point, BEP can be calculated by using this equation:

(3.7)

Where; FC = Fixed cost VC = Variable cost P = Profit

61 3.5.5

Calculation of Break Even Analysis

3.5.5.1 Price of Raw Material and Product Ethylene Oxide = RM 6.62 / kg or 0.001 tonnes metric Butanol = RM 9.00 / kg or 0.001 tonnes metric Butyl Cellosolve = RM 16.52 / kg or 0.001 tonnes metric Butyl Carbitol = RM 16.52 / kg or 0.001 tonnes metric (approximate similar with Butyl Cellosolve) (Source: World Chemical Report and MATRADE, 2010) 3.5.5.2 Utilities Electricity = RM 0.2810 / kWh (peak period) or RM 0.1730 / kWh (off- peak period) (Source: MIDA) 3.5.5.3 Rate Ethylene Oxide = 8502 kg / hr Butanol = 9241 kg / hr Butyl Cellosolve = 1.258 x 104 kg / hr Butyl Carbitol = 4775 kg / hr (Source: Mass Balance and Energy Balance) 3.5.5.4 Estimation of Capital Investment From the information from the Shell Chemicals Canada Ltd of Calgary, in order to run an Ethylene Glycol plant near Fort Saskatchewan, Alberta, Canada in partnership with Mitsubishi Chemicals of Japan, the company spent approximately RM 700 millions to RM 800 millions which produce 400,000 tonnes annually of Ethylene Glycol in year 2000. So, the fixed cost investment is RM 800 millions. (Source: World Chemical Report)

62 By considering the changes in economic conditions, some modifications have been made by using the following expression:

(3.8) Where; C2 = New capital investment C1 = Existing capital investment I1 = Chemical Engineering Plant Cost Index for 2010 = 527.9 I2 = Chemical Engineering Plant Cost Index for 2000 = 395 Source: Chemical Engineering Cost Estimation New capital investment for 100,000 tonnes metric per year of Butyl Cellosolve for 2000, C1

=

= RM 200 millions To evaluate fixed cost investment in 2010, C2

= RM 200 millions x

= RM 267.29 millions

63 3.5.5.5 Estimation of Total Fixed Cost

Total fixed cost = Operating labor + Maintenance and Repair cost + Insurance cost + Overhead cost + Operation supplies + Direct supervising and clerical labor + Laboratory charges + Local taxes (Source: Coulson and Richardson’s, Chemical Engineering, Volume 6, 2001) 2.5.5.5.1 Operating Labor

(3.9) Where; NOL = number of operators required to run the process unit per shift NON = number of operators needed to provide the shifts P = number of processing steps involving the handling of particulate solids NNP = number of non-particulate processing step handling

Type of Equipment

Number of Equipment

NNP

Reactor

1

1

Mixer

2

-

Heater

1

1

Distillation Column

4

4

Total

6

64 NOL = [6.29 + 31.7(0)2 + 0.23(6)]0.5 = 2.77 operators per shift = approximately 3 operators Pay for 1 operator per month = RM 1,500 Pay for 1 operator per year, PO = RM 18,000 (After considering bonus and allowance) (Source: MIDA) Assumptions: Plant performed 3 shifts per day and running 24 hours per day Operation days per year = 351 days 1 year = 52 weeks Minimum 1 operator rest for 2 weeks per year Weeks can be obtained by one operator per year = 50 weeks

x

So, shifts needed for plant in a year =

x

So, 1 operator can obtain shifts =

= 1053 shifts / year

x

= 250 shifts / year

Operators needed in a plant by considering the working shift, NON:

=

x

= 4.212 operators or approximately 5 operators

3.5.5.5.2 Operating Labor Cost, COL COL = NOL x NON x PO = 3 x 5 x RM 18,000 = RM 270,000 3.5.5.5.3 Direct Supervisory, DS and Clerical Labor, CL (10 to 25% of COL) CDS & CL =

x COL = 0.25 x RM 270,000 = RM 67,500

3.5.5.5.4 Maintenance and repairs, MNR (2 to 10% of fixed capital investment) CMNR =

x C2 = 0.1 x RM 267.29 x 106 = RM 26,729,000

65 3.5.5.5.5 Operation Supplies, OS (10 to 20% of MNR) COS =

x CMNR = 0.2 x RM 26.729 x 106 = RM 5,345,800

3.5.5.5.6 Laboratory Charges, LC (10 to 20% of OL) CLC =

x COL = 0.2 x RM 270,000 = RM 54,000

3.5.5.5.7 Pattern & Royalties, PR (0 to 6% of total product cost, Y) CPR =

x Y = 0.06 Y

3.5.5.5.8 Overhead cost, OVH (50-70% of OL, DS&CL and MNR) COVH =

x (COL + CDS & CL + CMNR) = 0.7 x RM (270,000 + 67,500 + 26,729,000)

= RM 18,946,550 3.5.5.5.9 Local Taxes and insurance, LTI (1.4 - 5% of C2) CLTI =

x C2 = 0.05 x RM 267.29 x 106 = RM 13,364,500

Type of Cost

Value (RM)

Direct

Labor

270,000

Maintenance and repair

26,729,000

Operation supplies

5,345,800

Direct supervising and clerical labor

67,500

66

Laboratory charges

54,000

Indirect

Local and Insurance taxes

13,364,500

Overhead

18,946,550

Pattern and Royalties

0.06 Y

TOTAL FIXED COST

64,777,350 + 0.06Y

3.5.5.6 Estimation of Total Variable Cost 3.5.5.6.1 Cost of raw materials, CRW Assume 2 weeks shut down for plant maintenance Butanol From material balance, the cost of Butanol for a production is:

x

x

x

= RM 700,615,656 / year

Ethylene Oxide From material balance, cost of Ethylene Oxide for a production is:

x

x

x

= RM 474,130,013 / year

Total cost of raw material = Cost (Butanol + Ethylene Oxide) =RM (700,615,656 + 474,130,013) / yr = RM 1,174,745,669 / yr

67 3.5.5.6.2 Utilities

The cost of utilities can be estimates as CUT: Electricity Price: RM 0.2810 / kWh (Source: Tenaga Nasional Berhad, MIDA) Total energy requirement = 296,938.2 kW From energy balance, the cost of electricity for a production is: Yearly Cost = 15,000 kWh

x

x

x

= RM 35,507,160 / yr

3.5.5.6.3 Total of Variable Costs, CVR Variables cost = Raw materials + Utilities CVR = CRW x CUT Subject

Value (RM / yr)

Raw Material Butanol

700,615,656

Ethylene oxide

474,130,013

Utilities Electricity

35,507,160

TOTAL VARIABLE COST

1,210,252,829

3.5.5.7 Estimation of General Expenses General expenses = Cost (Administrative + Distribution And Selling + Research and Development) 3.5.5.7.1 Administrative Cost, AD (40 to 60 % of operating labor) CAD =

x COL = 0.6 x RM 270,000 = RM 162,000

3.5.5.7.2 Distribution and Selling costs, D&S (2 to 20% of total product cost, Y) CD&S =

x Y = 0.2 x Y = 0.2Y

68 3.5.5.7.3 Research and Development cost, R&D (3% of total product cost, Y) CR&D =

x Y = 0.03 x Y = 0.03Y

So, General Expenses, GE = RM (162,000 + 0.2Y + 0.03Y) = RM 162,000 + 0.23Y 3.5.5.8 Total Product Cost Total Product Cost, Y = Total Fixed cost + Total Variable cost + General Expenses Y = RM [(64,777,350 + 0.06Y) + 1,210,252,829 + (162,000 + 0.23Y)] Y = RM 1,275,192,179 + 0.29Y Y = RM 1,796,045,323 Type of cost

Value (RM)

Direct Labor

270,000

Maintenance and repair

26,729,000

Operation supplies

5,345,800

Direct supervising and clerical 67,500 labor Laboratory charges

54,000

Indirect Local and Insurance taxes

13,364,500

Overhead

18,946,550

Pattern and Royalties

107,762,719

TOTAL FIXED COST

172,540,069

Subject

Value (RM / yr)

Raw Material Butanol

700,615,656

Ethylene oxide

474,130,013

Utilities

69 Electricity

35,507,160

TOTAL VARIABLE COST

1,210,252,829

General Expenses, GE = RM (162,000 + 0.2Y + 0.03Y) = RM 162,000 + 0.23Y = RM 162,000 + 0.23 (RM 1,796,045,323) = RM 413,252,424.30 3.5.5.9 Cost of Manufacturing Cost of manufacturing, COM = Total Variable Cost + General Expenses = RM 1,210,252,829 + RM 413,252,424.30 = RM 1,623,505,253 3.5.5.10 Break Even Point Variable cost per metric tonnes Butyl Cellosolve, VC

x

= = RM 12,102.53 / tone

Selling Price, SP for Butyl Cellosolve, SP =

x

x

= RM 1.652 x 109 / year Butyl Cellosolve price per tonne, P = RM 1.652 x 109 = RM 16520 / tone

x

70

Break even point can be calculated as follows: Break even point, =



= 39,058.57 = Approximate 39,059 tonnes per annum Butyl Cellosolve

Sample calculations for break even analysis For capacity = 10,000 tonnes of Butyl Cellosolve

1) Calculation for Total Revenue (TR) Q = 10,000 tonnes P = RM 16,520 / tonne TR = Q x P = 10,000 tonnes x RM 16520 / tonne = RM 165,200,000 = RM 1.652 x 108

2) Calculation for Variable Cost (VC) Q = 10,000 tonnes V = RM 12,102.53 / tonne VC = V x Q = RM 12,102.53 / tonne x 10,000 tonnes = RM 121,025,300

3) Calculation for Fixed Cost (FC) FC = RM 172,540,069

4) Calculation for Total Cost (TC) FC = RM 112,398,655 VC = RM 68,408,380 TC = FC + VC = RM 172,540,069 + RM 121,025,300 = RM 293,565,369

* Calculations is shown in Appendix C

71 Table 3.9: Break Even Analysis Capacity,

Fixed

Cost, Variable

Total Revenue, Total Cost, FC +

tonnes

FC

Cost, VC

TR

VC

0

172,540,069

0

0

172,540,069

10000

172,540,069

121025300

165200000

293,565,369

20000

172,540,069

242050600

330400000

414,590,669

30000

172,540,069

363075900

495600000

535,615,969

40000

172,540,069

484101200

660800000

656,641,269

50000

172,540,069

605126500

826000000

777,666,569

60000

172,540,069

726151800

991200000

898,691,869

70000

172,540,069

847177100

1156400000

1,019,717,169

80000

172,540,069

968202400

1321600000

1,140,742,469

90000

172,540,069

1089227700

1486800000

1,261,767,769

100000

172,540,069

1210253000

1652000000

1,382,793,069

Cost, RM

Break Even Graph 1,800,000,000 1,600,000,000 1,400,000,000 1,200,000,000 1,000,000,000 800,000,000 600,000,000 400,000,000 200,000,000 0

Fixed Cost Total Cost Total Revenue

Capacity, tonnes Figure 3.10: Break Even Graph

72 3.5.5.11 Payback Period Analysis In order to estimate the payback period of profit from the total investment of the plant, the discounted cash flow needs to be calculated respectively. It is important to know when the plant profit will be getting back after a few year operations.

73

End

Investment,

of

Depreciatio

FCI – Σdk

Revenue, R

n, dk

year,

Cost

of (R-

COM- Cash Flow

Manufacturing,

dk) x (1-t) +

COM

dk

-

-

Cumulative Cash Flow

k 0

(2,091,000,00

-

0)

1

(267,290,000)

1,917,524,2

-

53

-

1,917,524,2

-

1,623,505,253

-

(2,091,000,00

(2,091,000,0

0)

00)

(267,290,000)

(2,358,290,0

53

2

(270,000)

-

1,917,524,2

00)

-

1,623,505,253

-

(270,000)

53

3

4

-

-

00)

3,853,504,85

1,534,019,4

1,652,000,0

0.50

02

00

613,607,761

920,411,641 1,652,000,0

1,623,505,253

-

368,164,656. 60

6

-

220,898,793. 90

552,246,985 1,652,000,0

1,623,505,253

1,623,505,253

00

331,348,191 1,652,000,0 00

817,304,911

817,304,911

(1,541,255,0 89)

00

5

(2,358,560,0

1,623,505,253

1,012892,38

1,012,892,38

(528,362,70

5

5

4)

804,265,746.

804,265,746.

275,903,042

1

1

679,089,762.

679,089,762.

8

8

954,992,805

74

7

-

110,449,397

220,898,794 1,652,000,0

1,623,505,253

00

8

-

176,719,035.

44,179,759

20

9

-

114,867,372

1,652,000,0

1,623,505,253

-

-

0

1,652,000,0

1,623,505,253

0

1,652,000,0

1,623,505,253

00

11

-

-

0

2,652,000,0

1,623,505,253

00

12

2,091,270,00

-

0

* Calculations is shown in Appendix C

585,207,775.

1,540,200,5

4

4

80

641536967.9

641,536,967.

2,181,737,5

9

48

588,963,054.

588,963,054.

2,770,700,6

2

2

02

2,327,313,88

2,327,313,88

5,098,014,4

9

9

91

2,327,313,88

2,327,313,88

7,425,328,3

9

9

80

154,274,212.

2,245,544,21

9,670,872,5

1

2

92

00

00

10

585,207,775.

0

2,652,000,0 00

1,623,505,253

75

Cost, RM

Payback Period Graph 11,000,000,000 10,000,000,000 9,000,000,000 8,000,000,000 7,000,000,000 6,000,000,000 5,000,000,000 4,000,000,000 3,000,000,000 2,000,000,000 1,000,000,000 0 -1,000,000,000 -2,000,000,000 -3,000,000,000

0

1

2

3

4

5

6

7

8

9

10

11

Year Figure 3.11: Payback Period Graph

3.6

SUMMARY

The selling price of Butyl Cellosolve is RM 16.52 / kg. Therefore, for one metric tonne the amount is RM 16,520 and the variable cost was found to be RM 12,102.53 per metric tonne. The fixed cost investment is RM 267.29 millions. From the calculated break even point, the desirable capacity needed for this plant to recover all the costs of operation is 39,059 metric tonnes of Butyl Cellosolve per year and will get the profit at around 5 to 6 years.

76 CHAPTER 4

SITE SELECTION

4.1

INTRODUCTION

The approach to the site selection study was developed to identify site opportunities with the least overall land use and environmental impacts. This approach was taken in order to minimize the cost of implementation and construction of the new power plant and associated infrastructure.

Site selection is the most important in considering a land to build Butyl Glycol Ethers Plant. Site selection should be based on the principle that the purpose of a good site is to provide safe and economical flow of materials and people. This selection is also need to make in order to choose the best site in industrial area which can contribute more profit and convenient. It also will consider for short and long term period and it will show the lifespan for the land usually. Lifespan of the land usually depends on natural setting, land size, effluent discharge and plant design.

77 4.2 4.2.1

FACTOR EFFECTING THE SITE SELECTION Raw Material Supply

The main point to select a good site is to make sure that the raw material that can be supplied is nearby with the main plant either raw material from the plant itself or the outside of the plant. It is because more economical and the availability of raw material can be guaranteed. 4.2.2

Transport Facilities

The transportation should be considered in selecting the land because it will affect the transportation of materials and products to and from plant. If practicable, a site should be selected that is closed at least two major forms of transport which are road, rail, waterway or a seaport and roadways. Air transport also usually considered in terms of convenient and efficient for the movement of personnel and essential of raw material.

The pipeline also considered as transportation. A good site will minimize the distance materials have to flow either to or from store or during processing. It separates the raw material unloading facilities from the product loading areas. Pipeline should be run parallel to the road system in the site plant. 4.2.3

Availability of Labour

Labour is needed to construct and operate the plant. Because of that, there is a need to have skilled and experienced worker brought in from outside the site. Local trade union customs and restrictive practices will have to be considered when assessing the availability and suitability of the labour for recruitment and training. This thing will be managed by a manager from Human Resource.

78 4.2.4

Availability of Utilities

There is a need to consider the cost of three major sources of utilities which are electricity or power plant, water supply and fuel. In Malaysia, the cost of fuel is same for all country but the cost of electricity and water supply are depends on the country tariff price itself. The electricity is used commonly for electrochemical processes, motors, lightings, and general uses. Water is very important when producing any chemical production and it usually uses at excessive rate. The water is required for the plant for general purpose and that will be a concrete reason why the plant should be located nearby banks of river. 4.2.5

Availability of Suitable Land

This consideration also needs to reflect on in order to make sure an emergency situation can be mitigate immediately. The distance between the site or location of plant and emergency unit such as police station, fire station and hospital are not very far because if any emergency call is made, any accident can be prevented on the time. 4.2.6

Environment Impact and Effluent Disposal

A waste is the thing that any industrial company need to consider by treat the waste either biological or mechanical method. All industrial processes have a possibility to produce waste products, and full consideration must be given to the difficulties and coat of their disposal. The disposal of toxic and harmful effluents need to follow the standard and quality that permitted by law or local regulations. 4.2.7

Local Community Consideration

The proposed plant must locate far away from residential area and acceptable to the local community. Full consideration must be taken so that the residence do not expose to the risk and dangerous impact. For heavy industry, Department of Environmental (DOE) Malaysia stated that it should be built 500 meter far from residential and three (3) kilometers also takes as consideration.

79 4.2.8

Climate

There is a need to think about adverse climatic conditions at site since it will increase costs, and stronger locations and base of plant will be needed at location subject to high wind loads and earthquake.

80

Table 4.1: Analysis of Selection Site in Malaysia

NO

COUNTRY

SELANGOR

JOHOR

NEGERI SEMBILAN

1

LOCATION

Klang

Tanjung Langsat

Sg. Gadut Industrial Park

2

WIDTH OF LAND

1-60 Acres

1,709.93 Acres

99.41 Acres

3

WIDTH FOR BUTYL GLYCOL ETHERS PLANT

~40 Acres

~40 Acres

~40 Acres

4

TYPE OF LAND

Industry and Agricultural

Light, Medium and Heavy industry

Light and medium industry only

81

5

SELLING PRICE PER SQ.FEET (RM)

33.00

14.00 – 16.00

6.00

6

LEASEHOLD/FREEHOLD

Freehold

Leasehold/Freehold

Freehold

RAW MATERIAL SUPPLY

Optimal Chemical (M) Sdn Bhd Km 106 Jalan Kuantan Kuala Terengganu 24300 Kerteh, Terengganu, Malaysia.

Optimal Chemical (M) Sdn Bhd Km 106 Jalan Kuantan Kuala Terengganu 24300 Kerteh, Terengganu, Malaysia.

Optimal Chemical (M) Sdn Bhd Km 106 Jalan Kuantan Kuala Terengganu 24300 Kerteh, Terengganu, Malaysia.

Tel: +609 830 7700/7200 Fax: +609 830 7797

Tel: +609 830 7700/7200 Fax: +609 830 7797

Tel: +609 830 7700/7200 Fax: +609 830 7797

7

8

TRANSPORT FACILITIES

1. Port Klang (~18.7km from site) 2. Shah Alam Highway (~ 23.5km from site) 3. About RM60 will be charged for each lorry to bring the raw material from Kerteh to Klang.

1. Johor Port Authority (~12.8 km from site) 2. International Airport Senai (~43km from site) 3. About RM120 will be charged for each lorry to bring the raw material from Kerteh

1. Port Klang (~120km from site) 2. North – South Highway (~102km from site) 3. About RM70 will be charged for each lorry to bring the raw material from Kerteh to Negeri Sembilan.

82 to Tanjung Langsat

9

AVAILABILITY OF LABOUR

5.4km from Pekan Meru 4.2 km from Kg. Batu Empat 3.0 km from Taman Klang Utama

24.6 km from Kg. Kong Kong 8.8 km from Taman Pasir Putih 7.7 km from Jalan Pasir Putih

6km from Taman Tuanku Jaafar 4 km from Taman Pinggiran Senawang 3.2 km from Seremban Jaya

AVAILABILITY OF UTILITIES

1. WATER

35m3 = RM 2.07/m3 >35m3 = RM 2.28/m3 (minimum payment = RM36)

0 – 20m3 =RM 2.22/m3 21 – 40m3=RM 2.96m3 >41m3= RM 2.96m3

10

2. FUEL

Petrol RON95: RM 1.75/L RON95 Fuel: RM 1.85/L RON97 : RM 2.05/L Diesel : RM 1.70/L

Petrol RON95: RM 1.75/L RON95 Fuel: RM 1.85/L RON97 : RM 2.05/L Diesel : RM 1.70/L

RM 1.00/m3

Petrol RON95: RM 1.75/L RON95 Fuel: RM 1.85/L RON97 : RM 2.05/L Diesel : RM 1.70/L

83

3. POWER

Tariff E2 Medium Voltage Peak/Off-Peak Industrial Tariff For each kilowatt of maximum demand per month during the peak period For all kWh during the peak period For all kWh during the offpeak period The minimum monthly charge is RM600.00 Tariff E2s - Special Industrial Tariff (for consumers who qualify only) For each kilowatt of maximum demand per month during the peak period For all kWh during the peak period For all kWh during the offpeak period The minimum monthly charge is RM600.00

RM/kW

sen/kWh

29.30

28.1

17.3 sen/kWh

25.2 RM/kW 25.8 sen/kWh 14.7 sen/kWh >900kWJ/Month =RM 44.60

84

AVAILABILITY OF SUITABLE LAND 11

12

ENVIRONMENTAL IMPACT AND EFFLUENT DISPOSAL

1. Police Station Kapar (~4.2 km) 2. Balai Bomba dan Penyelamat Pelabuhan Klang (~ 11 km) 3. Tengku Ampuan Rahimah Hospital (~11km)

The effluent is must to treat first either by using biological (aerobic and anaerobic pond treatment) or by using mechanical type (example is activated carbon). Sometimes, the effluent can become sludge and can discharge the some amount of water after treatment. But

1. Police Station Taman Pasir Putih (~9.3km) 2. Police Station Masai (~15km) 3. Balai Bomba dan Penyelamat Johor Jaya (~26km) 4. Sultanah Aminah Hospital (~30km)

The effluent is must to treat first either by using biological (aerobic and anaerobic pond treatment) or by using mechanical type (example is activated carbon). Sometimes, the effluent can become sludge and can discharge the some amount of water after treatment. But

1. Police Station Paroi (~5.5km) 2. Hospital Tuanku Jaafar (~7.4 km) 3. Balai Bomba Senawang (~3.6 km) 4. Balai Bomba dan Penyelamat Seremban (~7.2 km)

The effluent is must to treat first either by using biological (aerobic and anaerobic pond treatment) or by using mechanical type (example is activated carbon). Sometimes, the effluent can become sludge and can discharge the some amount of water after treatment. But usually, the

85 usually, the water is used usually, the water is used through circulation mode through circulation mode which means the plant is which means the plant is operate in recycle mode by operate in recycle mode by using that water to operate using that water to operate the processes involved. the processes involved. Before the water is discharge Before the water is discharge at final discharge point, the at final discharge point, the sample of water is always sample of water is always taken by an officer of DOE taken by an officer of DOE and examines the sampling at and examines the sampling at Jabatan Kimia Negeri. Jabatan Kimia Negeri. Usually, many of industry Usually, many of industry always must comply with always must comply with Standard B which means the Standard B which means the water will be discharge far water will be discharge far from the residence water from the residence water source. source. For the plant, usually the scheduled waste includes many things and the disposal of this need to follow Environmental Quality (Scheduled Wastes) Regulations 2005. The company need to follow standard of disposal based on

For the plant, usually the scheduled waste includes many things and the disposal of this need to follow Environmental Quality (Scheduled Wastes) Regulations 2005. The company need to follow standard of disposal based on

water is used through circulation mode which means the plant is operate in recycle mode by using that water to operate the processes involved. Before the water is discharge at final discharge point, the sample of water is always taken by an officer of DOE and examines the sampling at Jabatan Kimia Negeri. Usually, many of industry always must comply with Standard B which means the water will be discharge far from the residence water source. For the plant, usually the scheduled waste includes many things and the disposal of this need to follow Environmental Quality (Scheduled Wastes) Regulations 2005. The company need to follow standard of disposal based on SW1 (Metal and MetalBearing Wastes), SW2 (Wastes containing

86

SW1 (Metal and MetalSW1 (Metal and MetalBearing Wastes), SW2 Bearing Wastes), SW2 (Wastes containing (Wastes containing principally Inorganic principally Inorganic Constituents which may Constituents which may contain metal and Organic contain metal and Organic Materials),SW3(Wastes Materials),SW3(Wastes containing principally containing principally Organic Constituents which Organic Constituents which may contain metal and may contain metal and Inorganic Materials), SW4 Inorganic Materials), SW4 (Waste which may contain (Waste which may contain both Inorganic both Inorganic and Organic and Organic constituents) constituents) and SW5 and (Other wastes). SW5 (Other wastes).

principally Inorganic Constituents which may contain metal and Organic Materials),SW3(Wastes containing principally Organic Constituents which may contain metal and Inorganic Materials), SW4 (Waste which may contain both Inorganic and Organic constituents) and SW5 ( Other wastes).

The nearby rivers are as follows: The nearby river is as follows: ~5.5km from the site plant (Sungai Kelang)

The nearby river is as follows: ~60km from site plant (Sungai Johor)

~36 km from the site (Sungai Timun Linggi) ~34.7 km from the site (Port Dickson Beach)

87

13

LOCAL COMMUNITY CONSIDERATION

5.4km from Pekan Meru 4.2 km from Kg. Batu Empat 3.0 km from Taman Klang Utama

24.6 km from Kg. Kong Kong 8.8 km from Taman Pasir Putih 7.7 km from Jalan Pasir Putih

6km from Taman Tuanku Jaafar 4 km from Taman Pinggiran Senawang 3.2 km from Seremban Jaya

June „10: 170 – 200 mm July ‟10 : 200 – 240 mm August ‟10: 200 – 240mm September ‟10: 140 – 200mm

June „10: 130 – 190 mm July ‟10 : 140 – 230 mm August ‟10: 110 – 230mm September ‟10: 150 – 240mm

32 Times ( Modified Mercalli Scale is VI)

14 Times ( Modified Mercalli Scale is V)

TPM Technopark Sdn Bhd Tel: 07 – 2226922 Fax: 07 – 224 2221 Email: techno@tpm technopark.com.my

Negeri Sembilan Investment Centre (NSIC) Tel: + 606 7659570/5981 Fax: +606 765 5982 Email: ceonsic @ns.gov.my

CLIMATE i.

RAINFALL

14

ii.

15

EARTHQUAKE (1909 – May 2010)

CONTACT PERSON

June „10: 160 – 200 mm July ‟10 : 110 – 210 mm August ‟10: 110 – 200mm September ‟10: 160 – 260mm

49 Times (Modified Mercalli Scale is VI)

Mohd Khair Parlan 019 – 641 5815 [email protected]

88

4.3

JUSTIFICATION ON SELECTION SITE FOR BUTYL GLYCOL ETHERS

PLANT 4.3.1

Site Evaluation

4.3.1.1 Klang, Selangor(Malaysia) Klang is the royal capital of state of Selangor and it is located within 32 km to the west of Kuala Lumpur and 6 km east of Port Klang. It has a big potential in industry light, medium or heavy industry because of its land characteristics and strategic location to get easiest supplies from outside. a) Marketing Area In producing a large amount of product of Butyl Glycol Ethers of 100,000 Metric Tonne Per Annum (MTA), there is a need to consider that location should be close enough in order to minimize the costs on transportation of material. Klang has a potential in developing the development of industrial sectors. b) Raw Material Supply The availability of raw material is the most important factor to select the site location for the plant. The raw material suppliers should be close enough in order to acquire raw material rapidly and easily. But unfortunately, both raw material needed by the process which are butanol and ethylene oxide only is produced by Optimal Chemical (M) Sdn. Bhd which located in Kerteh, Terengganu. The distance between Kerteh and Klang will be about 360 km (4 hours 34 minutes). c) Transport Facilities Transportation should be practicable. Since the cost of transportation on land is inexpensive, it is always prefer this type of transportation to bring the raw material to the site. About RM70.00 is charged per lorry for each trip. But this value can still negotiable. Air transport should be avoided because both raw materials are dangerous and explosive.

89 d) Availability of Labour Klang has higher population and this will be an advantage to find the labor and skills labors easily because of Klang are well-known as developing area nowadays. e) Utilities Water supply will be important utility and the plant usually uses a huge volume of water. In that sense, Klang area should be a good site since water supply can get from SYABAS Sdn. Bhd. While electricity source can obtain from TNB Malaysia. f) Environmental Impact and Effluent Disposal The proposed site is far from residential area and any disposal of effluent should be monitored and managed always in order to follow the regulation properly. For this case, Department of Environmental (DOE) Shah Alam has a power to monitor and administer that regulation of scheduled waste and effluent. g) Local Community Consideration Based on „Penilaian Awal Tapak (PAT)‟ which conducted by DOE, the heavy industry like this should be built on the land that far from residential area by 500 meter and sometimes 3 kilometers also take as consideration. h) Type of Land The land for built the plant should be flat and stable. Because of the land is suitable for agricultural and industry, it is not recommended to built the plant on it because ability to withstand of land will be lower and lifespan of land is shorter.

i)

Climate

Based of Malaysia Meteorological Department Report 2010, the intensity of earthquake in Malaysia has about 49 of frequency that happen in Selangor from 1909 to May 2010. Any special features for plant construction due to the change of excessive weather change are not necessary.

90 4.3.1.2 Tanjung Langsat, Johor (Malaysia) a) Marketing Area Since this land is still new for industrial purposes, it is suitable to grab this opportunity to get this fine land. Although the raw material supplier which is Optimal Chemical (M) Sdn. Bhd. is quite far from the site, it still the best choice to choose this land. b) Raw Material Supply Both raw material needed by the process which are butanol and ethylene oxide only is produced by Optimal Chemical (M) Sdn. Bhd which located in Kerteh, Terengganu. The distance between Kerteh and Tanjung Langsat will be about 442 km (6 hours 8 minutes). c) Transport Facilities There should be at least two type of transportation is needed to bring in or out the plant. Johor Port Authority only about 18.7 kilometers from the site and this Port can be used to export the product from the plant and but still the land transportation is the best choice to minimize the costs compared to air or water route. d) Availability of Labor Either outside or the resident nearby is capable to become a labor. Skills or unskilled labor can get from residential area and can train them properly for build-up the chemical plant and operate it. e) Utilities Utility of water supply can get from Syarikat Air Johor Sdn Bhd at lower tariff. For electricity, this plant need high power source to operate some equipment and this electricity can obtain from TNB Malaysia.

91 f) Environmental Impact and Effluent Disposal The proposed site is far from residential area (over 500 meters) and any disposal of effluent should be monitored and managed always in order to follow the regulation properly. For this case, Department of Environmental (DOE) Johor has power to monitor and administer that regulation of scheduled waste and effluent. g) Local Community Consideration Based on „Penilaian Awal Tapak (PAT)‟ which conducted by DOE, the heavy industry like this should be built on the land that far from residential area by 500 meter and sometimes 3 kilometers also take as consideration. h) Type of Land This land has width about 1,709.93 acres .This show that there is enough space to built this plant that only need about 40 acres. This land is the best choice for industrial purposes.

i)

Climate

Stronger location and base of plant should be consider very carefully and Tanjung Langsat has medium level of rainfall reading and the frequency of earthquake in Johor from 1909 to May 2010 shows 32 with intensity maximum of VI.

92 4.3.1.3 Sungai Gadut Industrial Park, Negeri Sembilan (Malaysia)

a) Marketing Area For the primary product Butyl Glycol Ethers is produced in bulk quantities per day, the location of site should be closed with marketing area to minimize the costs. b) Raw Material Supply The availability of raw material is the most important factor to select the site location for the plant. Both raw materials (Ethylene Oxide and Butanol) can only obtained from Optimal Chemical (M) Sdn. Bhd which located in Kerteh, Terengganu. The distance between Kerteh and Sungai Gadut Industrial Park will be about 398 km (5 hours 6 minutes). c) Transport Facilities For land transportation, normally charged for RM70 from Kerteh to Sungai Gadut Industrial Park, Seremban, Negeri Sembilan. It is takes about 5 hours and 6 minutes (398 km) to reach at destination via East Cost Expressway. d) Availability of Labor The residential area nearby can be potential labor to work at the plant for operate and build-up purpose. The examples close residential areas are Taman Tuanku Jaafar (about 6 km), Kampung Sungai Gadut (about 1.5 km) , Kampung Ulu Rantau Sungai Gadut (about 4 km) and so on. e) Utilities Huge volume of water source may be needed to over run the process. Jabatan Air Negeri Sembilan has responsible to supply the water to all needs at prescribed tariff. Tenaga Nasional Berhad (TNB) Malaysia is responsible to supply the electricity.

93 f) Environmental Impact and Effluent Disposal The proposed site is far from residential area (over 500 meters) and any disposal of effluent should be monitored and managed always in order to follow the regulation properly. For this case, Department of Environmental (DOE) Johor has power to monitor and administer that regulation of scheduled waste and effluent. Before discharge any waste, it should be comply with the standard that stated by DOE. g) Local Community Consideration Based on „Penilaian Awal Tapak (PAT)‟ which conducted by DOE, the heavy industry like this should be built on the land that far from residential area by 500 meter and sometimes 3 kilometers also take as consideration. h) Type of Land This type of land is not the best choice because the geographical condition of land only suitable for light and medium industry only. i)

Climate

Malaysia lies on the equatorial lines, which made weather hot and sometimes humid. Naturally, tornado or earthquake does not occur in Malaysia. There is not necessary to provide any special facilities and construction to withstand with excessive climate. Negeri Sembilan has a maximum intensity of earthquake of V and frequency of 14.

94

Figure 4.1:

Development of Tanjung Langsat Industrial Complex, Johor (MIDA, 2008)

95 Table 4.2: Factor rating method for determination of the best suitable location for a new plant

Critical Success Factor

Weight (%)

Scores (out of 100)

Klang

Tanjung Langsat

Weighted Score Sg.Gadut Industrial

Klang

Park

Tanjung

Sg.Gadut

Langsat

Industrial Park

Strategic Location

35

75

90

80

(0.35x75)=26.25

(0.35x90)=31.5

(0.35x80)=28

Price of Land

10

75

80

85

(0.10x75)=7.5

(0.10x80)=8.0

(0.10x85)=8.5

Marketing Area

10

80

70

75

(0.10x80)=8.0

(0.10x70)=7.0

(0.10x75)=7.5

Land Available

8

55

90

80

(0.08x55)=4.4

(0.08x90)=7.2

(0.08x80)=6.4

12

80

70

70

(0.12x80)=9.6

(0.12x70)=8.4

(0.12x70)=8.4

Transportation

11

80

85

80

(0.11x80)=8.8

(0.11x85)=9.35

(0.11x80)=8.8

Availability of Labor

6

80

80

85

(0.06x80)=4.8

(0.06x80)=4.8

(0.06x85)=5.1

5

75

70

80

(0.05x75)=3.75

(0.05x70)=3.5

(0.05x80)=4.0

Type of Land

3

55

90

75

(0.03x55)=1.65

(0.03x90)=2.7

(0.03x75)=2.25

Total Score

100%

74.75

82.45

78.95

Raw Material Supply

Community Considerations

96

4.4

CONCLUSION

This project entitled production of Butyl Glycol Ethers 100 000 matrix tone/year. The capacity of the product produced is huge. The product is in bulk. The location has to be close to the primary market in order to cut cost in transportation of the product. Butyl Glycol Ether has been used for more than half a century. Today it is used extensively in both water- and solvent-based coatings and industrial and consumer cleaners. Cleaners made with Butyl Glycol Ether can remove oils, fats, waxes, greases and baked-on or ground-in residues from floors, walls, glass, metal parts, and equipment. Cleaning products which may contain Butyl Glycol Ether include general surface cleaners, floor strippers, window cleaners, spot cleaners, rust removers and ink and resin removers. Paints and coatings that use Butyl Glycol Ether range from lacquers, varnishes and enamels to water-based coatings and inks.

Since the end product is the raw material for various industries, it will be best to place the plant in an industrial area near to these industries. For marketing wise area, Port Klang is suggested since there are various industries there.

The location also has to be near to the raw material supply. Closeness to raw material supply is important to have the ability to obtain the raw material in reasonable and best price and to cut cost on transportation. Butyl Glycol Ether main raw material is basically hydrocarbons group. The available site locations to obtain the raw materials are most definitely at Tanjung Langsat, Johor. The transport facilities are important since the plant needs accessibility to get raw materials supplies, to transport end products, to get cheap labor, experts‟ accessibility and so much more. Malaysia‟s transportation facilities are one of the most advanced in South East Asia. The three major transportation links are by air, by land and by ports. Usually by air is not a wise choice to transport raw material and products since it is very costly and dangerous. By land and by port is the most popular and wise choice since it is economics. There few places that are suitable Klang and Tanjung Langsat because it is near to the Port, have railway tracks and have easy access to the highway. Availability of labor can be measured by the number of population in that area. Labors are required to construct the plant and also to operate it later on .The local labors

97 usually being hired to do medium-skilled or low-skilled job requirements. For high skilled jobs, outsiders will be recruited. This will come back to the importance of transport facilities. Place like Klang are suitable since this place has high number of population and it‟s easy to get experts there. Because of Tanjung Langsat is well established in chemical and petrochemical based industries, there is a lot of experts there.

Availability of utilities included the availability of water, electricity, fuel and so much more. Utilities are important to run the processes in the plant. Usually, a plant owned electricity generators to generate electricity for their own usage. This will save their cost in long term. The plant has to be located somewhere there is easy to get water supplies. Anywhere in Malaysia with water pipeline are suitable to be the location of the plant. Water is important for cooling processes, general process use and so much more. And usually, industrial park will provide the required utilities. While reasonable priced fuel needed to generate steam and power. There is no doubt that Tanjung Langsat is suitable since it has sufficient water supply and fuel with reasonable price.

Availability of suitable land means the availability of land for the proposed plant and future expansion. The land also has to be well drained, flat and have suitable load bearing characteristics. The site need to be evaluated carefully to make sure that there is ample space for the plant and future expansion. Environmental impact and effluent disposal on a location basically involves on the local regulations on managing the industrial waste and the process by-product. Full consideration must be made on the costs and difficulties to dispose the wastes. From this point of view, a place with similar industries should be chosen assuming that in that particular area, a proper waste and by-product managements were developed. Tanjung Langsat have efficient and established waste management company.

Local community considerations involve the acceptation from the local community. The plant should be in a location where it doesn‟t give any threat to the local community. And to develop a new plant, the facilities available in the local community should be evaluated. These facilities are to take care of the labours welfare. The facilities include the banks, schools, housing areas, mosques, hospitals and so much more. The location of the plant must at least around 30 minutes from the nearest town.

98 Tanjung Langsat has main advantage for this factor since Tanjung Langsat is quite near to Singapore and Johor Bahru.

Malaysia can be said a harmony and peaceful country with strong political stability. And looking at this factor, the all the proposed sites considered as suitable. But when it comes to taxes, Tanjung Langsat is one of the cheapest taxes and building or development of a new plant is most welcome by Johor government.

By evaluating from factor to factor, Tanjung Langsat has a lot of advantages compared to others. Tanjung Langsat is still developing and have around 4000 acre of land still available. It is obvious that the most suitable site location for this plant is in Tanjung Langsat. This can be proven by using the factor rating method to evaluate and assess the sites.

99 CHAPTER 5

PROCESS SAFETY AND PLANT LAYOUT

5.1

Introduction

The production of this plant is to produce Ethylene Butyl Glycol Ether where it can be produce by n-butanol and ethylene oxide. The co-products are diethylene butyl glycol ether, triethylene butyl glycol ether and tetraethylene butyl glycol ether.

Organizations have their own legal and moral responsibility to concern about the health and welfare of their employees and public. All manufacturing processes are hazardous, but in chemical processes there are additional, special, hazards associated with the chemicals used and the application of sound engineering practices that the risks are reduced to acceptable levels. Safety and loss prevention in process design can be considered through identification and assessment of the hazards, control of the hazard and process and limitation of the loss (Crowl, 2002).

100 5.2

Plant safety

Safety cannot be successfully implemented unless with certain serious consideration by both plant management and workers at the plant. Most successful accident prevention programs have been resulted from management„s demonstrated interest and active participation. Thus, the management„s point of view at safety significantly influences the employee„s attitude towards safety. In fact, the ultimate success of any safety program depends upon the awareness of the plant workers.

Safety and loss prevention in process design can be considered under the following broad headings which are identification and assessment of the hazards, control of the hazards materials, and control of the process. Prevention of hazardous deviation in process variables such as pressure, temperature, flow by provision of automatic control system interlocks, alarm system, trips, together with good operating practices and management also limitation of the loss. The damage and injury caused in an incident occurs, pressure relief, plant layout, provision of fire fighting equipments. (Sinnott, 2003)

101 5.2.1 Chemical storage

Proper chemical storage controls health and physical hazards posed by chemical compounds during storage in the laboratory and also in plant especially when handling the ethylene oxide which is hard to handle. Proper design is needed to protect flammables from ignition, minimize the potential of exposure to poisons and segregate incompatible compounds to prevent their accidental mixing via spills, residues, earthquakes, fires or human errors.

N-butanol is being transferred by pipeline from Kerteh to our plant at Tanjung Langsat, Johor. For n-butanol storage tank, the n-butanol is located at tank farm. Tank farms are provided facilities such as refineries and chemical plants for n-butanol storage and handling systems.

Typically, tanks and pipeline are above ground. In general, fire protection for gasoline tanks is sufficient enough. Furthermore, n-butanol tanks provided extra precaution is made for leaking detection and toxic hazard.

For the time being, ethylene oxide is being transported by road tankers. The road tankers must meet the requirement on design for the road tankers such as earthing connections shall be provided to prevent dangerous differences in electrical potential arising between the carrying tank, body of the vehicle, the piping and ground during the filling or discharging of the chemicals. It must also include the insulating material that will demonstrate minimum reactivity when in contact with ethylene oxide and be suitable for operating at the lowest ambient temperatures to be met in service.

102 5.3

Safety of workers

A safe and healthier work environment is one of the minimum requirements which are both legally and ethically desirable. However, this will not happen by chance but concerted effort should be made on the part of everyone in the company to work towards this end. A safer and healthier work place is not only desirable but it also minimizes cost and improves productivity. By making the work environment safe, the job and the people safe, an organization can achieve its ethical, legal and financial goals. Workplace safety is a category of management responsibility in places of employment.

The management has responsibilities for the health and safety of their workers. They are also responsible for any visitors entering their premises such as customers, suppliers and the general public. The responsible are in those following:

Ensure that plant and machinery is safe to use, and standard operation procedures are always followed. Take precautions against the risks caused by flammable or explosive hazards, electrical equipment, noise and radiation. Ensure safe workplace. Make sure that ventilation, temperature, lighting, and toilet, washing and rest facilities all meet health, safety and welfare requirements. Prevent risks to health. Prevent or control exposure to substances that may damage health. Make sure all materials are stored in safe conditions and handle with care. Provide adequate first aid facilities. Tell the workers about any potential hazards from the work do, chemicals and other substances used by the firm, and give information, instructions, training and supervision as needed in setting up emergency plans. Avoid potentially dangerous work involving manual handling and if it cannot be avoided, take precautions to reduce the risk of injury. Provide health supervision as needed. Provide protective clothing or equipment free of charge if risks cannot be removed or adequately controlled by any other means.

103 Ensure that the right warning signs are provided and looked after at all time. Report any accidents, injuries, diseases and dangerous occurrences to either the Health and Safety Executive (HSE) or the local authority, depending on the type of business.( Flynn, 2002)

104 5.4

Emergency Response Plan

5.4.1 Introduction

An emergency at plant may occur without warning. Proper planning for emergencies is necessary to minimize the impact on plant operations. This plan is designed to ensure preparation of the plant is proper handled when emergencies occur. When an emergency occurs, the production will be interrupted. Therefore, it is essential to have appropriate plans and trained personal to overcome the situation in an effective and proper way. The plan must contain procedures for notifying appropriate personnel, defines responsibilities, and provides guidelines for handling emergencies (Backhurst, 1973).

5.4.2 Objectives

The on-site emergency plan prepared the procedures for dealing with emergency situations involving loss of containment in general terms. In brief, the main points for inclusion are:

Arrangements for training staff in duties they will be expected to perform; arrangements for informing local authorities and emergency services; and arrangements for providing assistance with off-site mediatory action. Containing and controlling incidents to minimize the effects and limit danger to person, environment and property; Communication is a crucial factor in handling an emergency. When an incident occurs, it is necessary to immediately raise the alarm, to declare an emergency and call the fire brigade, tackle a fire or control spills and leaks when it is safe to do so. Implementing

the

measures

necessary

to

protect

person

and

environment; Description of actions should be taken to control the conditions at events and to limit their consequences, including description of equipments and resources available;

105 Evacuate the site, and if necessary nearby premises, to inform the works emergency services and threatened areas within the works and the neighboring areas. The emergency procedures include instructions for dealing with fires, leaks and spills (Backhurst, 1973).

106 5.4.3 Items for consideration in an emergency action plan

When dealing with emergency, there are several items need to be considered to ensure the emergency response plan will achieve their goals. At this plant, there are several essential points that need to be highlighted and reminded for every worker. Shut down and start-up procedures. Map of the facility layout. Every land area in this plant is equipped with facility that used for emergency cases. Thus, the workers must ensure that they know what to do when handling any emergencies. Emergency organization chart with phone numbers and addresses. Every plant has their safety officers that will monitor the whole plant. But for any types of emergency, it is advisable to call the fire station. Risk assessment of expected emergencies. List of outside agencies with phone numbers and addresses. Identification and location of alarm systems. Every section of equipment is equipped with alarm. If the workers are suspect unusual with the process, the workers must use the alarm and next procedures will proceed. Identification of the location of key emergency equipment, supplies, shelters, assembly areas, evacuation routes and communication also command center. It is advisable to assemble at the assembly point to avoid any injuries. Safety is priority ( Backhurst, 1973). 5.5

n-Butanol

As n-Butanol is main reactant in EGBE production, it is important to handle this material with safer way. n-Butanol is flammable liquid and vapor. Emergency response plan are designed in event of prevention of chemical spill and in event of fire caused by n-Butanol.

Effective spill prevention programs involve process engineering controls, standard operating procedures, spill response planning, and periodic training geared to each employee‟s degree of involvement in the response actions. Engineering controls associated with n-Butanol storage tanks include overfill protection by means of visible

107 and audible high-level alarms; secondary containment systems, such as dikes, bunds, vapor detectors and alarms; and explosive gas detectors to detect and warn of fire and explosion hazards in the event of a release.

n-Butanol is stored in a dikes, well-ventilated containers that shall be tightly closed when not in use. The containers must also store out of direct sunlight and on an impermeable floor. Always open containers slowly in order to allow any excess pressure to vent. Try to avoid breathing the hazardous vapor and contacting with eyes, skin or clothing. After handling such this chemical, wash thoroughly with soap and water. Any contaminated leather clothing need to be destroyed to avoid any reaction and make sure to decontaminated soiled clothing thoroughly before re-use. 5.5.1

Emergency response plan in event of spill occurs

Several steps to take if a spill occurs are: Evacuate all persons who not wearing protective equipment from the area of the spill or leak until clean up is complete. Stop or reduce the release of material, if it can be done safely. Eliminate all sources of ignition. Notify and evacuate supervisor or emergency coordinator of any spill of harmful vapors. For large spills and fires, immediately call the fire department. Do not walk through spilled product. Avoid skin contact and inhalation. Stay upwind and keep out of low-lying areas. Key elements of essential protection are immediate and appropriate response and maintaining control of the fire.

Fire events, though undesirable, are preferable to explosion events. Process hazard analysis must consider which is more likely in each circumstance: a fire or an explosion. If the judgment is explosion, then consideration should be given to changing circumstances, process conditions, or process configuration, so that fire is the most likely consequence of ignition.

If this is not an option, then it is essential that all potential ignition sources be eliminated and that no mobile ignition sources are allowed to enter the area.

108 Extinguishing media to be use for small fires are carbon dioxide (CO 2) or dry chemical. For large fires occurs, aqueous film forming foam is used. Users must thoroughly decontaminated bunker gear and other fire-fighting equipment before re-use.

Water may be ineffective but should be used to cool fire-exposed structures and vessels. Water spray is use for large fires. If potential for exposure to vapors or products of combustion exists, must wearing full fire fighting turn out gear and NIOSH approved self-contained breathing apparatus. Oxidizing chemicals may accelerate the burning rate in fire situation. Vapor is heavier than air and can travel considerable distance to a source of ignition and flashback (Celanese, 2004).

For disposal considerations, dispose of spilled material in accordance with state and local regulations for hazardous waste. For n-Butanol, the recommended methods for disposal are by incineration process or biological treatment at a federally or state permitted disposal facility (Celanese, 2004).

5.6

Ethylene Oxide

Ethylene oxide is another raw material in this plant to produce Ethylene Glycol Butyl Ether. Emergency response plan are designed in release of ethylene oxide as this chemical having high toxicity. Thus, in the event of release the steps should be taken are:

Notify the safety department. Employees engaged in correcting emergency conditions will wear respirators until the emergency is controlled. Evacuate the area. Do not re-enter the area until re-entry is cleared by the safety department.

109 5.8.1 Hazard identification Ethylene oxide may cause cancer and has high toxicity by breathing. It is also extremely flammable and may cause genetic damage. Ethylene oxide may irritating to eyes, respiratory system and skin because of liquefied gas and will cause cold burns and frost bite if contact with liquid 5.6.2 First aid measures

5.6.2.1

Inhalation

Inhalation of ethylene oxide may cause toxicity in bodies. In low concentration, it may cause narcotic effects. Symptoms may include faintness, headache, vomiting and loss of co-ordination. Take victim to uncontaminated area and wearing self contained breathing apparatus. Keep the victim warm and rested. Call a doctor and apply artificial respiration if breathing stopped. 5.6.2.2

Skin and eye contact

May cause chemical burns to skin and cornea (with temporary disturbance to vision). Remove contaminated clothing. Soak affected area with water for at least 15 minutes. Wash out eyes thoroughly with water for at least 15 minutes. Obtain medical assistance. 5.6.3 Fire fighting measures Exposure to fire may cause containers to rupture or explode. Incomplete combustion may form carbon monoxide. All known extinguishes can be used. 5.6.3.1

Specific methods

Stop the product‟s flow if possible and continue water spray from protected position until container stays cool. Do not extinguish a leaking gas flame unless absolutely necessary. Spontaneous or explosive may occur within the time. Extinguish any other fire and move the container away and cool with water from a protected position.

5.6.3.2

Special protective equipment for fire fighters

Use self contained breathing apparatus and chemically protective clothing.

110 5.6.4 Accidental release measures 5.6.4.1

Personal precautions

Evacuate area and eliminate ignition sources to ensure adequate air ventilation. Use self-contained breathing apparatus and chemically protective clothing. Do not smoke while handling product. Always keep self contained breathing apparatus in case of emergency and always wearing working gloves and safety shoes while handling gas cylinders.

5.6.4.2 Environmental precautions Try to stop the chemical release. Prevent from entering sewers, basements and workpits or any place where its accumulation can be dangerous to environment. 5.6.4.3 Clean-up methods Ventilate and keep the area evacuated and free from ignition sources until any spilled liquid has evaporated.

5.6.5 Handling and storage Make sure the equipment is an adequately earthed. Prevent suck back of water into the container. Air from the system must be purged before introducing the gas. Do not allow backfeed into the container. Only use properly specified equipment which is suitable for ethylene oxide supply pressure and temperature. Prevent bottles from falling down and segregate from oxidant gases and other oxidants in store. Make sure the containers always been kept below 50°C in well ventilated place.

5.7

Standard Operating Procedures

As both of the raw materials are flammable and combustible liquid, safety operating procedures must always be followed in handling both chemicals.

Safety shielding is required at any time in a risk of explosion, splash hazard or highly exothermic reaction. Portable shields, which provide protection to all laboratory

111 occupants, are acceptable. Manipulation of flammable liquids outside of a fume hood may require special ventilation controls in order to minimize exposure to the material.

Avoid discharge this chemical to atmosphere and do not discharge into any place where its accumulation could be dangerous. Toxic and corrosive gases may be formed during combustion should be scrubbed before discharge to atmosphere. Do not discharged ethylene oxide into areas where there is a risk of forming an explosive mixture with air. Waste gas should be burst through a suitable burner with flash back arrestor.

In charger should ensure to follow all national and local regulations and need to ensure their operators understand about the flammability and toxicity hazard disposal. Users of breathing apparatus must be always trained and before handling or using this chemical they must have thorough safety study even as proper care has been taken in the preparation.

5.8

Hazards and operability study (HAZOP)

A systematic qualitative procedure to identify process hazards and potential operating problems using a series of guide words to study process deviations. HAZOP is used to question every part of the process to discover what deviations from the objective of the design may occur and what type of causes lead to the problem and consequences.

This is done systematically by applying suitable guide words and technique for either batch or continuous plants which can be applied to new or existing processes to identify hazards. This is a set of formal hazard identification and elimination procedures designed to identify hazards to people, process plants and the environment.

Therefore, the potential hazard can be determined. In effect, HAZOP studies assume that a hazard can arise where there is a deviation from the design or operating intention. Corrective action can then be made before a real accident occurs.

112 The prime objective of HAZOP study was to examine the proposed design and identify the safer process before design is hardened by physical construction, hazards or potential operational problems which can be avoided by redesign or suitable operating procedures. Selected lines and plant items in the P&ID were examined in turn by applying appropriate guide terms.

The potentially hazardous situations and consequences were evaluated. Measures to eliminate or minimize the undesirable consequences are recommended. The results of step by step procedure and the recommendations were entered in the HAZOP minute sheets.

5.8.1 Main recommendations of the HAZOP Install alarm (temperature, pressure, level, flow, composition) on each product line to column to ensure higher operating efficiency is maintaining the product specification. Do regular maintenance and inspection to all equipment to avoid any equipment breakdown. 5.8.2 Advantages of HAZOP study to design application Identifies need for emergency procedures to mitigate. Early identification of problems areas when conceptual design stage. Identified and effectiveness of safety systems. Provide essential information for safety case, such as on the hazards Identifies

need

for

commissioning,

operating

and

maintenance

procedures for safe and reliable operations. Through examination of hazard and operability problems when applied at detailed stage. Meets governmental requirements.

113

5.9

Ethylene Glycol Butyl Ether

5.9.1 Other names: CAS No. 111-76-2 Ethylene glycol monobutyl ether Ethylene glycol butyl ether (EGBE) Butyl glycol ether 2-Butoxy-1-ethanol 2-Butoxyethanol Butyl CELLOSOLVE solvent

5.9.2 Hazard Identification

Ethylene glycol butyl ether is clear colourless liquid and its primary routes of entry to skin contact, eyes, inhalation, and accidental ingestion. There are several effects of exposure if contacted to skin whereby it may cause irritation. Prolonged exposure may result in the material being absorbed through the skin with possible systemic effects. If contacted to eyes, it may cause irritation, stinging, tearing, redness, and swelling. It also may cause irritation to the respiratory tract, coughing, dizziness, nausea if contacted to inhalation. For chemical contacted to ingestion, it may cause irritation to the gastrointestinal tract and may cause nausea, vomiting, diarrhea. Persons who are involving with pre-existing skin disorders, eye problems, respiratory or lymphoid system function may be more susceptible to effects of overexposure. 5.9.3 First Aid Measures

If this chemical is contacted to skin, rinse affected area with plenty of water. Remove and wash clothing before wearing again and seek for medical attention if irritation continues. If it is splashed into or surround the eyes, immediately flush eyes gently with running water for 15 minutes or until material is gone. After 5 minutes remove contact lens, if present, and then continue washing. Seek medical attention if irritation persists. In case of contacted with inhalation, remove to fresh air. Seek for medical attention if irritation persists. If chemical contacted with ingestion, please rinse mouth with water,

114 give several glasses of water. Never give anything by mouth to an unconscious person. Do not persuade vomiting. If vomiting occurs naturally, have victim lean forward to decrease risk of aspiration. Seek for medical attention if stomach upset continued occurs. All the general precautions need to be monitored and looking for the protection advices from the First Aid Providers.

5.9.4 Fire Fighting Measures Flash Point and method for Ethylene Glycol Butyl Ether is almost more than 180°F PMCC. Lower Explosive Limit (LEL) for EGBE is 10.6% and Upper Explosive Limit (UEL) for EGBE is 1.1%. Autoignition temperature for EGBE is commonly 472°F. The extinguishing media that will give the reaction with EGBE are water fog, carbon dioxide, alcohol-resistant foam and dry powder.

Above 142°F, an explosive vapor/air mixture may form in poorly ventilated areas. Under fire conditions that can develop explosive pressures, the containers need to be sealed and cool the containers with water spray. NFPA ratings for EGBE are Health: 1, Flammability: 0 and Reactivity 0

5.9.5 Accidental Release Measures Spill or leak procedures of controlling EGBE are firstly, remove the chemical‟s spill by using commercial absorbent material, such as STARDUST Super Absorbent, wet dry vacuum, or mop. Dispose in compliance with applicable governmental regulations. For large spills, form a dike, as with sorbent socks, to limit spreading. Pump into salvage tank for treatment or disposal. Recover usable material by any practical method. As a precaution, dilute the spill residue with plenty of water. 5.9.6 Handling and Storage Use good industrial practice in storage for storage precautions of EGBE. EGBE itself need to be store in a closed container at room temperature. As a general safety precaution, store away from heat sources, sparks or open flames.

115

5.9.7 Exposure Controls and Personal Protection Personal Protective Equipment used to protect spillage of EGBE is including for respiratory, hands, eyes, skin and also for industrial hygiene as well. For respiratory protection, if to be used for a prolonged period in a confined area, use NIOSH/MSHA approved respiratory protection. For hands, use rubber or plastic gloves. For eyes prevention, chemical goggles in compliance with OSHA need to be used. And for skin, wear suitable protective clothing. Wash clothing separately before wearing again. The important prevention need to be care of is wash after handling, especially before eating, drinking or smoking.

5.9.8 Stability and Reactivity For stability and reactivity of these EGBE, it can be concluded that EGBE is stable, but above 142°F, an explosive vapor or air mixture may form in poorly ventilated areas and this conditions might resulted in a hazardous situation and strong oxidizing agents. Fire conditions or extremely high temperatures could result in the production of such toxic oxides as those of carbon, phosphorous, and sodium but hazardous polymerization will not occur in this reaction. EGBE is not carcinogenic chemical and having LC50>750mg/L.

5.9.9 Waste Disposal Throughout this part, there are two types of waste disposal need to be follow by EGBE user or producer. There are product disposal and packaging disposal. For both product and packaging disposal, it needs to be disposing in accordance with federal, state, and local regulations.

116 5.10 Diethylene Glycol Butyl Ether 5.10.1 Other names • CAS No. 112-34-5 • 2-(2-Butoxyethoxy) ethanol • Diethylene glycol monobutyl ether • Butyl CARBITOL™ solvent • Diethylene glycol butyl ether (DGBE) • Butoxydiglycol • Diglycol monobutyl ether • Butyl diglycol ether

5.10.2

Product Description

Diethylene glycol butyl ether (DGBE) is a sort of glycol ether. It is mainly used as a solvent in coatings, inks, cleaners and specialty fluids, or to fabricate diethylene glycol butyl acetate. It is clear, liquid with a mild ether odour and evaporates slowly and completely water soluble. Although some glycol ethers have been shown to cause bad reproductive effects and birth defects in laboratory animals, DGBE does not show the same model of toxicity as these other glycol ethers. DGBE has low oral, dermal and inhalation toxicity. At a standstill, DGBE can cause severe eye irritation and slight corneal injury when improperly used. Occupational and consumer exposure is possible because DGBE is used in a extensive range of industrial and consumer products like cleaning products, paints, and inks. Skin exposure is the mainly way for human exposure. DGBE studies show it is unlikely to cause unpleasant environmental impact because it readily biodegrades, does not bioaccumulate and has low acute toxicity to aquatic organisms.

117 5.10.3 Manufacture of Product

DGBE is produced by reacting two ethylene oxide molecules with normal butanol (nbutanol) using a catalyst. If the ratio of ethylene oxide to n-butanol is greater than two, tri-ethylene glycol monoethers are produced along with the DGBE.

5.10.4 Product Uses

DGBE is used as a solvent in coatings and cleaner applications for industrial and consumer markets. It is also used as a chemical intermediate to produce diethylene glycol monobutyl ether acetate (DBA) and some herbicides, insecticides and plasticizers. DGBE is also used in hydraulic brake fluid applications. Particularly, Butyl CARBITOL solvent is used as:

Deactivator and stabilizer for agricultural pesticides. Latex coalescent in water-based architectural and industrial coatings. Primary solvent in solvent-based silk screen printing inks. Coalescent for latex adhesives. Coupling solvent for resins and dyes in water-based printing inks. Diluents in hydraulic brake fluid applications. Solvent for ball point and felt tip pen inks, and textile dyeing and printing. Coupling agent and solvent in household and industrial cleaners, rust removers, hard surface cleaners and disinfectants.

118 5.10.5 Exposure Potential

DGBE is used in the production of industrial and consumer products. Based on the uses for DGBE, the public could be exposed in the course of:

Workplace exposure Exposure can arise either in DGBE manufacturing facility or in the different industrial or consumer product manufacturing amenities that use DGBE. Each manufacturing or application facility should have suitable work processes and safety equipment guiding principles in place in order to limit unnecessary DGBE exposure.

Consumer exposure to products containing DGBE DGBE is not selling for direct consumer use, but it is used as a constituent in coatings, paints, cleaners, adhesives, pesticides, etc. Consumers will have got in touch with with DGBE. The most likely route for human exposure is skin exposure. In order to help avoid from unnecessary exposure, product labels need to be reviewed and all instructions and guidelines for proper use must always be followed.

Environmental releases In the incident of a spill, the focal point is on containing the spill to prevent contamination of soil, surface or ground water. For tiny range of spills, DGBE should be absorbed with materials such as sand or vermiculite. This stuff is considered conveniently non-toxic to aquatic organisms on an acute basis. Low vapor pressure helps in reducing inhalation risk. Conversely, adequate ventilation is recommended to control airborne levels below any exposure guidelines. Keep away the chemical from heat, sparks and flame. Consult the relevant SDS for more information about protective equipment and procedures.

Large release Industrial spills or releases are irregular and are generally contained. If large spills occur, the material should be captured, collected and re-processed, or disposed of according to applicable governmental requirements. If DGBE is present in a fire

119 situation, it can produce carbon monoxide (highly toxic) and carbon dioxide (an asphyxiant at sufficient concentrations). Containers may burst from gas generation in a fire situation. Fire-exposed containers are cooled by using water spray until danger of re-ignition has passed.

Violent steam generation may occur upon application of direct water stream to hot liquids. Deny any unnecessary entry into the area and consider the use of unmanned hose holders. Use of a direct water stream may spread fire. Immediately withdraw all personnel from the area in case of rising sounds from venting safety device or discolorations of the container. Emergency personnel should wear proper protective equipment, including self-contained breathing apparatus (SCBA), and always follow the emergency procedures carefully. The community should be notified of the hazards associated with the specific release event when it is relevant in scale or risk.

Health Information DGBE has low acute oral, dermal and inhalation toxicity, and it is also not a skin sensitizer. DGBE can cause harsh eye irritation and minor corneal injury when improperly used. Prolonged contact may cause slight skin irritation with local redness, but is unlikely to result in absorption of harmful amounts. High oral repeated doses in rats caused red blood cell damage as well as changes in the liver, kidneys and stomach. DGBE has not been found to be mutagenic, teratogenic, fetotoxic or neurotoxic. It did not cause birth defects, interfere with reproduction or show toxicity to fetuses. However, body weights of newborn animals were decreased. The major metabolite of DGBE is 2-(2-butoxyethoxy) acetic acid (BEAA). Both DGBE and BEAA are excreted primarily in the urine following DGBE oral, dermal and intravenous exposure in rats. Environmental Information DGBE is non-toxic to aquatic organisms on an acute basis. It is readily biodegradable and does not bioaccumulate meaning that does not build up in the food chain. DGBE moves to water when it is released because of its high solubility, low volatility and high soil mobility. It degrades quickly in water. Because of these properties, DGBE poses a low risk to the environment. Ethylene glycol ethers have only uncommonly been measured in the environment, and when found, their concentrations are generally in the low part-per-billion (ppb) range.

120 Physical Hazard Information DGBE is stored in carbon steel, stainless steel or phenolic-lined steel drums. It cannot be stored in aluminum, copper, galvanized iron or galvanized steel. Avoid contact the chemical with strong acids, strong bases and strong oxidizers. DGBE can oxidize at elevated temperatures and thermally stable at typical use temperatures, but can oxidize at elevated temperatures. It should not be distilled to dryness, as it may form peroxides. Decomposition can cause gas generation and pressure in closed systems. Thermal decomposition products can include and are not limited to aldehydes, ketones and organic acids. Spills of DGBE on hot, fibrous insulations may result in spontaneous combustion by lowering the auto-ignition temperatures. . Regulatory Information Governmental requirements may exist that govern the manufacture, sale, transportation, use and/or disposal of DGBE. These requirements may vary by city, state, country or geographic region. Information may be found by consulting the relevant Safety Data Sheet.

121 5.11

Triethylene Glycol Butyl Ether

5.11.1

Other information CAS NO: 143-22-6 FORMULA: C4H9(OCH2CH2)3OH MOL WT: 206.28 SYNONYMS: Triglycol Monobutyl Ether; Butoxytriglycol; BTG;2-(2-(2Butoxyethoxy)ethoxy)ethanol;3,6,9-rioxatridecan-1-ol; Butyl Triglycol Ether; PHYSICAL STATE: clear liquid MELTING POINT: -48°C BOILING POINT: 265°C (Decomposes) SPECIFIC GRAVITY: 0.985-1.000 SOLUBILITY IN WATER: miscible FLASH POINT: 156°C STABILITY: stable under ordinary conditions

5.11.2

Applications of Triethylene Glycol Butyl Ether

Glycol ethers, with the arrangement of ether, alcohol and hydrocarbon chain in one molecule, offer versatile solvency characteristics with both polar and non-polar properties. The chemical structure of long hydrocarbon chain resist to solubility in water, whereas ether or alcohol groups introduce the promoted hydrophilic solubility performance. This surfactant-like structure provides the compatibility between water and a number of organic solvents, also ability to couple unlike phases. Glycol ethers are characterized by their wide range of hydrophilic or hydrophobic balances. Glycol ethers are used as diluents and leveling agents in the manufacture of paints and baking finishes.

Triethylene glycol butyl ether is used in the manufacture of nitrocellulose, oils, gums, dyes, soaps, grease, paint removers, metal cleaners,polymers and combination lacquers. They are used as an additive in brake fluid and formulated for dying textiles, leathers also for insecticides and herbicides. They provide performance in cleaners products with oil-water dispersions. They are also used in printing industries and having slow evaporation rate, used as an adhesive for perfumes, germicides, bactericides, insect repellents, and antiseptic, also used as an additive for jet fuel to prevent ice buildup.

122 5.12

Ethylene Glycol

5.12.1

Hazard Identification

5.12.1.1 Potential Acute Health Effects Ethylene glycol is a hazardous material in case of ingestion. It is slightly hazardous in case of skin contact such as irritant, permeator of eye contact and inhalation. Severe overexposure to this type of chemical can result in death.

5.12.1.2 Potential Chronic Health Effects The carcinogenic effect for ethylene glycol is fall under A4 category which is not classifiable for human or animal by ACGIH. It is mutagenic for mammalian somatic cells but nonmutagenic for bacteria or yeast. For developmental toxicity of this chemical is the substance may be toxic to kidneys, liver, central nervous system (CNS). Repeated or prolonged exposure to the substance can produce target organs harm. Repeated exposure to a highly toxic material may produce general deterioration of health by an accumulation in one or many human organs.

5.12.2

First Aid Measures

5.12.2.1 Eye Contact Check for and remove any contact lenses. In case of contact, flush eyes with plenty of cold water for at least 15 minutes immediately. Get medical attention if irritation occurs.

5.12.2.2 Skin Contact Wash the infected skin with soap and cold water. Cover the irritated skin with an emollient. Get medical attention if irritation expands.

5.12.2.3 Inhalation If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention immediately.

123 5.12.2.4 Ingestion Do not persuade vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. If large quantities of this material are swallowed, call a physician immediately. Loosen all tight clothing such as a collar, tie, belt or waistband to make the victim easy to breathe.

5.12.2.5 Serious Ingestion Persons with pre-existing kidney, respiratory, eye, or neurological problems might be more sensitive to Ethylene Glycol. Elimination of Ethylene Glycol may be achieved by the following methods: Emptying the stomach by gastric ravage. It is useful if initiated within < 1 of ingestion. Correct metabolic acidosis with intravenous administration of sodium bicarbonate, regulating the administration rate according to repeated and frequent measurement of acid or base status. Administer ethanol (orally or by IV (intravenously)) or fomepizole (4methylpyrazole or Antizol)) therapy by IV as an antidote to inhibit the formation of toxic metabolites. If patients are still diagnosed and treated early in the course with the above methods, hemodialysis may be avoided if fomepizole or ethanol therapy is efficient and has corrected the metabolic acidosis, and no renal failure is present.

However, once severe acidosis and renal failure occurred, hemodialysis is necessary. It is effective in removing Ethylene Glycol and toxic metabolites, and correcting metabolic acidosis.

124 5.12.3

Accidental Release Measures

5.12.3.1 Small Spill: Dilute the chemical spill with water and mop up, or absorb with an inert dry material and place in an appropriate waste disposal container. Finish cleaning the spill by spreading water on the contaminated surface and dispose to local and regional authority requirements. 5.12.3.2 Large Spill: Stop leak if without risk. Do not get water inside container. Do not touch spilled material. Use water spray to reduce vapors. Avoid entry into sewers, basements or confined areas; dike if needed. Remove all ignition sources. Call for assistance if any problem regarding on disposal. Finish cleaning by spreading water on the contaminated surface and allow evacuating through the sanitary system. Be careful that the product is not present at a concentration level above TLV. Check TLV on the MSDS and with local authorities. 5.12.4

Handling and Storage

5.12.4.1 Precautions Keep away from heat. Keep away from sources of ignition. Empty containers pose a fire risk; evaporate the residue under a fume hood. Ground all equipment containing material. Do not ingest or breathe gas, fumes, vapor or spray. Wearing suitable protective clothing is compulsory. If ingested, seek for medical advice immediately and show the container or the label. Keep away from incompatibles such as oxidizing agents, acids, alkalis. 5.12.4.2 Storage Keep container tightly closed and place container in a cool, well-ventilated area.

125 5.12.5

Exposure Controls/Personal Protection

5.12.5.1 Engineering Controls Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors below their respective threshold limit value. Ensure that eyewash stations and safety showers are proximal to the work-station location. 5.12.5.2 Personal Protection Personal protective equipment need to be wear such as safety glasses, synthetic apron and impervious gloves. For most conditions, no respiratory protection should be needed. However, if material is heated or sprayed and if atmospheric levels exceed exposure guidelines, an approved vapor (air purifying) respirator need to be used. 5.12.5.3 Personal Protection in Case of a Large Spill For large spill of chemical, personal protective equipment is much more important. Splash goggles, full suit, boots, and gloves are needed. Suggested protective clothing might not be sufficient; consult a specialist before handling this product.

5.12.5.4 Solubility Ethylene glycol is soluble in cold water, hot water and acetone but slightly soluble in diethyl ether. It is miscible with lower aliphatic alcohols, glycerol, acetic acid, acetone and similar ketones, aldehydes, pyridine, similar coal tar bases.

5.12.5.5 Chronic Effects on Humans May cause bad reproductive effects and birth defects (teratogenic) based on animal test data. No human data has been reported at this time. It may affect genetic material (mutagenic). There are several acute potential health effects regarding to this type of chemical itself. If spill at skin, it may cause skin irritation and also may cause more severe response if skin is abraded. A single prolonged exposure is not likely to result in material being absorbed through skin in harmful amounts. Immense contact with damaged skin may result in absorption of potentially harmful amounts. If contacted to eyes, vapors or mist may cause temporary eye irritation (mild temporary conjunctival inflammation) and lacrimation.

126 Corneal injury is unlikely or insignificant. It is rapidly absorbed from the gastrointestinal tract. Oral toxicity is expected to be moderate in humans due to Ethylene Glycol even though tests with animals show a lower degree of toxicity. Excessive exposure such as swallowing large amounts may cause gastrointestinal tract irritation with nausea, vomiting, abdominal discomfort, and diarrhea. It can affect behavior and central nervous system within 0.5 to 12 hours after ingestion.

A temporary inebriation with excitement, daze, headache, slurred speech, ataxia, somnolence, and euphoria, similar to ethanol intoxication, can occur within the first several hours. As the Ethylene Glycol is metabolized, metabolic acidosis and further central nervous system depression such as convulsions and muscle weakness develop. Serious intoxication may develop to coma associated with hypotonia, hyporeflexia, and less commonly seizures, and meningismus within 12 to 24 hours.

127 5.13

Diethylene Glycol

Diethylene Glycol (DEG) is a straight-chain dihydric alcohol aliphatic compound terminated on both ends by a hydroxyl group. It is a clear, water-white, practically odorless, hygroscopic liquid at room temperature.

5.13.1 Application • Unsaturated polyester resins • Polyester polyols • Lubricant and coupling agents • Plasticizers • Humectants and dehydrating agents • Solvents

Diethylene glycol used as dehydrating agent for natural gas, raw material for production of plasticizers and polyester resins, humectants, textile lubricant and coupling agent, solvent in textile dyeing and printing, constituent of hydraulic fluids, plasticizer for paper, cork and synthetic sponges, solvent in printing inks, raw material for the production of esters used as emulsifiers, demulsifiers, and lubricants, selective solvent for aromatics in petroleum refining. 5.13.2 Product Safety Policy

The Material Safety Data Sheet (MSDS) should always be read and understood thoroughly before handling the product and adequate safety procedures should be followed. Information on toxicity, environmental and industrial hygiene aspects of the products may be found in the MSDS. Precautionary measures also included only use with adequate ventilation, avoid breathing vapor, mist or gas, avoid contact with eyes, skin and clothing, keep container closed and the important thing is wash thoroughly after handling.

128 5.13.3 Handling and storage

Diethylene glycol (DEG) is stable, non-corrosive chemical with high flash point. It has a tendency to increase in color and acidity, accompanied by drop in pH upon long-term storage. Peroxides may also form causing difficulties when DEG is used as a chemical intermediate. To minimize this quality deterioration, DEG need to be stored in stainless steel, aluminum or suitably lined such as vinyl type lining like Amercoat 23 or equivalent, tank under an inert gas pad which is preferably nitrogen. For temperatures below +40°F, low-pressure stainless steel steam coils need to be provided in storage tanks and steam or electrical tracing of insulated transfer lines to form ease pumping. Temperatures above 120°F must avoid in preventing product towards degradation. Flushing with water and steam can readily clean transfer or storage tanks.

Pumps should be constructed of stainless steel where very low iron content is compulsory. Pressed asbestos gaskets are recommended for pumps. Cast-iron or centrifugal pumps with stainless shafts and impellers are satisfactory while rubber-lined or rubber-bound gaskets should be avoided. Flexible graphite filled or stainless steel double-jacketed gaskets are usually efficient in handling larger gaskets. Stainless steel winding with flexible graphite filler piping gaskets performs well. Pipe thread lubricants based on corrosion inhibiting zinc compounds or graphite based lubricant with aluminum are generally satisfactory, but, glycols are excellent penetrants and leaks may be present where hydrostatic testing has indicated a tight system. Therefore, the system should be rechecked after the glycol has been added. Using of white lead, glycerin, and Teflon tape pipe dopes are suitable.

129 5.14

Triethylene glycol

5.14.1 First Aid Measures

For eye contact, check for and remove any contact lenses. Flush infected eyes immediately with running water for at least 15 minutes by keeping eyelids open and cold water may used. Do not use an eye cream. If affected area become worst, seek for medical attention immediately. If spillage contacted to inhalation, allow the victim to rest in a well ventilated area and seek immediate for medical attention if infection continued. Do not induce vomiting if the chemical contacted with ingestion. Loosen the tight clothing such as a collar, tie, belt or waistband. If the victim is not breathing, perform mouth-tomouth resuscitation. Seek for immediate medical attention immediately. 5.14.2 Accidental Release Measures

In accidental release measures, it is covered two types of spills which are small spill and large spill. For small spill, the chemical were diluted with water and moped up, or absorb with an inert dry material and place it in an appropriate waste disposal container. Finish cleaning the spillage by spreading water on the contaminated surface and dispose the waste according to local and regional authority requirements.

For large spill, absorb with an inert material and put the spilled material in an appropriate waste disposal. Finish cleaning the spillage by spreading enough water on the contaminated surface and allow it to evacuate through the sanitary system. 5.14.3 Handling and storage

There are several precautions in handling and storage the chemicals. In order to avoid from accident, keep away the chemical from heat and also from ignition sources. Empty containers cause a fire risk; evaporate the residue under a fume hood. Ground all equipment containing material. Do not swallow or breathe the gas, fumes, vapour or spray. Avoid chemical contact with eyes. If ingested, seek for medical advice immediately and show the container or the label.

130 For storage of the chemical, keep the container in dry and cool place. Ground all equipment containing material. Keep container tightly closed and in a cool, well-ventilated place. Combustible materials should be stored away from extreme heat and away from strong oxidizing agents.

5.14.4 Exposure control and personal protection

For engineering controls, provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors below their respective in threshold limit value. Ensure that eyewash stations and safety showers are proximal to the work-station location. Use splash goggles and lab coat as common laboratory rules. While handling chemical in case of a large spill, it is compulsory to wear splash goggles, full suit, boots, and gloves. Suggested protective clothing might not be sufficient, consult a specialist before handling this product.

131 5.15

Tetraethylene Glycol

5.15.1 First Aid Measures

There is a lot of possibility towards an accident while handling this type of chemical. If the chemical splashed to the skin, wash the infected area with plenty of water. Remove contaminated clothing and do not reuse until thoroughly laundered. If it is splashed to the eyes, wash eyes with plenty of water, holding eyelids open and seeking for medical assistance promptly if there is irritation. Remove the victim from contaminated area promptly to avoid chemical contacted with inhalation but please remember that the rescuer must not endanger himself. If breathing stops, administer artificial respiration and seek medical aid promptly.

If contacted with ingestion, give plenty of water to dilute product. Do not induce vomiting because inadvertent inhalation of vomited material may seriously damage the lungs. The danger of this is greater than the risk of poisoning through absorption of this relatively low toxicity substance. The stomach should only be emptied under medical supervision, and after the installation of an airway to protect the lungs. Keep victim quiet. If vomiting occurs, lower victim‟s head below hips to prevent inhalation of vomited material and seek for medical help promptly. 5.15.2 Protective equipment and personal measures

There is no special mechanical ventilation, hand protection and clothing required while handling this chemical but safety glasses with side shields must always wear to protect the eyes.

5.15.3 Handling and storage

Tetraethylene Glycol is hygroscopic and need to be store in a dry environment and away from oxidizing agents. Always ensure that the containers, whether empty or full, or part full, are tightly sealed unless in use. Avoid breathing product mist. Never cut, drill, weld or grind on or near this container. Avoid contact with skin and wash work clothes frequently. An eye bath and safety shower should be available near the workplace.

132 5.15.4 Spill procedures When there is a leaking of chemical, some precautions need to be considered which is dyke to control spillage and prevent environmental contamination. In handling the spill in ventilate contaminated area; recover free liquid with suitable pumps, absorb residue on an inert sorbent, sweep and pick up using plastic or aluminum shovel. It is also need to be stored in closed containers for recycling or disposal. 5.15.5 Disposal For waste disposal, do not flush to sewer; recycle solvent if possible, if local regulations permit may be put in sanitary landfill, may be incinerated in approved facility after mixing with a suitable flammable waste. For waste in containers, drums should be reused. Recondition and pressure test by a licensed reconditioner prior to reuse. Pails must be vented and thoroughly dried prior to crushing and recycling. For chemical dispose in IBCs (intermediate bulk containers), polyethylene bottle must be pressure tested & recertified at 30 months. It should be replaced at 60 months (5yrs) and steel containers must be inspected, pressure tested and recertified every 5 years. Never cut, drill, weld or grind on or near this container, even if empty.

5.15.6 Environmental information

This product is highly water soluble and cannot be bioaccumulate. This product degrades readily in the presence of oxygen which is 23% degradation in 20 days without bacterial “acclimation” 88% in 20 days after ~50 days “acclimation”. Degradation this product reacts with atmospheric hydroxyl radicals and estimated half life in air is 8 hours. It is also extremely low vapour pressure suggests that this will be a minor route for degradation. This product is also water soluble and moves readily in soil and water.

133 CHAPTER 6

MASS BALANCE

6.1

Introduction

The wanted production of Ethyelene Glycol Butyl Ether is known to be 300 metric ton per day. The raw materials used are ethylene oxide and butanol. Butanol purity is around 99.7wt% while ethylene oxide is assumed to be 100wt% pure and the compositions of product in the crude product is known 75wt% EGBE, 20wt % of DEGBE, 4.75wt% of TEGBE and the rest is the residues (McKetta & John J, 1984). Ethylene oxide is assumed to be fully consumed with the presence of excess butanol.

Besides glycol ethers, this process also produces glycol as by-product. Glycols are produced by reaction of ethylene oxide and water. Water was present in butanol. Glycol will be distilled along with the product. The compositions of MEG, DEG and TEG is assumed to be 85wt% MEG, 10wt % of DEG, 3wt% TEG and 2wt% of higher glycols since the process and details to produce glycol ethers and glycols is considered to be similar (Weissermel & Arpe, 1978). For complete reaction and to ensure the products are still in liquid form, the mass of butanol feed must be large enough than the mass of ethylene oxide.

134

6.2

Main Reaction

Reaction 1 Ethylene Oxide

Butanol

Ethylene Glycol Butyl Ether, EGBE

Reaction 2 Ethylene Oxide

EGBE

Diethylene Glycol Butyl Ether. DEGBE

Reaction 3 Ethylene Oxide

DEGBE

Triethylene Glycol Butyl Ether. TEGBE

Reaction 4 Ethylene Oxide

DEGBE

Tetraethylene Glycol Butyl Ether. TetraEGBE

135

6.3

Side Reaction

Reaction 5 Ethylene Oxide

Water

Monoethylene Glycol MEG

Reaction 6 Ethylene Oxide

MEG

Diethylene Glycol DEG

Reaction 7 Ethylene Oxide

DEG

Triethylene Glycol TEG

Reaction 8 Ethylene Oxide

TEG

Tetraethylene Glycol TetraEG

Assumptions:

Ethylene oxide fully react to produce products Purity of butanol is 99.7wt% Ethylene oxide is pure. Steady state condition.

136

Production amount of EGBE

6.4

Sample calculation

6.4.1

Mass balance on reactor

Mass Flow Temp Pressure

5118.4 kmol/hr 120 oC 40 bar

Conversion Reactor

Mole Flow, kmol/hr Butanol Water EO EGBE

4783 136.52 193 5.8814

Mass Flow Temp Pressure

4925.4 kmol/hr 137.13 oC 39.8 bar

Mole Flow, kmol/hr Butanol 4638.3 Water 136.52 EO 193 EGBE 112.03 DEGBE 29.433 TEGBE 8.6850 TetraEGBE 0.4319 Impurities very small = 0

137

i)

By using extent of reaction

a)

Balance on ethylene oxide (limiting reactant)

Equation I

Since,

is 193 kmol/hr and the conversion of the reaction 1 is 75% is 193 – 193(0.75) = 48.25 kmol/hr

So, b)

Balance on butanol

Equation II

Since,

is 4783 kmol/hr and the conversion of the limiting reactant in this reaction is

75% So,

is 4783 – 193(0.75) = 4638.25

From Eqn II,

c)

= 144.75

Balance on EGBE

Equation III

Since,

is 5.881 kmol/hr and the conversion of the limiting reactant in this reaction

1 and 2 are 75% and 80% respectively. Base on the stoichiometry of the reaction So, from eqn III

is 5.881 + 144.75 – 38.6 = 112 kmol/hr

138

All the calculation repeats same method as above to get

Table 6.1: Summary of the reaction process

Outlet reactor

conversion of limiting reactant

EGBE 144.75

EGBE 106.2

75%

DEGBE 38.6

DEGBE 29.43

20%

TEGBE 9.168

TEGBE 8.686

4.75%

TetraEGBE

TetraEGBE

0.4316

0.431

Inlet reactor

EO 193

+

EO 48.2

+

EO 9.6

+

EO

+

0.432

Butanol 193



EGBE 48.2



DEGBE 9.6



TEGBE



0.432

0.25%

139

6.5

Sample Calculation

6.5.1

Mass balance on Distillation Column 1

Mass Flow Temp Pressure

345401.44 kg/hr 121.79oC 1.3 bar

Mass Fraction Butanol Water EGBE Mass Flow Temp Pressure

0.991 0.0072 0.0018

366190.34 kg/hr 137.13oC 39.8 bar

Mass Fraction Butanol 0.9386 Water 0.068 EGBE 0.0362 DEGBE 0.0131 TEGBE 0.0049 TetraEGBE 0.00033

Mass Flow Temp Pressure

19266.384 kg/hr 195.25oC 1.5 bar

Mass Fraction EGBE DEGBE TEGBE TetraEGBE

0.6528 0.2478 0.093 0.0062

140

Equation 1 Equation 2

We have all the value of total mass flow rate and mass fraction of Feed stream. So, we can determine unknowns by doing some calculation on component balance and total balance.

a)

Balance on Butanol

From eqn 2, with

=0

D = 345401 kg/hr From eqn 1 we got B = 19266 kg/hr

b)

Balance on EGBE

From eqn 2, with

=0

We got = 0.653

Same calculation for other component

For impurities is very small to be consider and calculate but value can be seen in Preliminary flow diagram PFD attached.

141 CHAPTER 7

ENERGY BALANCES

7.0

Energy Balances

The values of heat capacities of the components are as following: (Obtained from McGraw-Hill Chemical Properties Handbook, Carl L.Yaws)

Table 7.1: Values of heat capacities of the components Component

Cp Formula

JMR

Cp A

Ethylene Oxide

C2H4O

44.05

34.57

Cp B

Cp C

Cp D

@25o C

4.29

-1.55E-

2.41

8.88

E-06

E+01

2.22

2.05

E-06

E+02

5.35

7.53

E-07

E+01

3.62

2.71

E-06

E+02

3.72

3.56

E-06

E+02

E-01 5.23

Butanol

C4H10O

74.122

127.21

E-01 -4.00

Water

H2O

18.015

92.053

E-02 1.04

EGBE

C6H14O2

118.2

126.347

E+00 1.21

DEGBE

C8H18O3

162.2

178.607

E+00

03 -1.54E03 -2.11E04 -2.96E03 -3.18E03

5.92 TEGBE

C10H22O4

206.28

E+02 7.07

TetraEGBE

C12H26O5

250.3

E+02

- 1.65 C2H6O2 MEG

62.07

75.878

6.42 E-01

E-03

1.66 1.69 E-06

E+02

142

DEG

TEG

TetraEG

C4H10O3 C6H14O4 C8H18O5

106.12

150.17

194.22

126.618

160.25

142.47

8.56

-1.95

1.87

2.58

E-01

E-03

E-06

E+02

1.21

-3.06

3.24

3.34

E+00

E-03

E-06

E+02

1.99

-4.96

5.09

4.29

E+00

E-03

E-06

E+02

Table 7.2: Boiling Point Temperature, Tb, Heat of Vaporization, Hv, Heat of Formation, Hf, SG and volume, V Component

Tb (K)

∆Hv (J/mol)

∆Hf (J/mol)

SG

V (m3/mol)

Ethylene Oxide

1.09E+01

2.57E+04

-5.26E+04

1.52E+00

2.90E-02

Butanol

1.18E+02

4.32E+04

-2.75E+05

8.11E-01

9.14E-02

Water

1.00E+02

4.07E+04

-2.85E+05

1.00E+00

1.80E-02

EGBE

1.71E+02

4.62E+04

-4.41E+05

9.00E-01

1.31E-01

DEGBE

2.31E+02

5.41E+04

-6.06E+05

9.55E-01

1.70E-01

TEGBE

2.83E+02

2.31E+04

-7.00E+05

9.89E-01

2.09E-01

TetraEGBE

3.04E+02

2.45E+05

-7.00E+05

9.95E-01

2.52E-01

MEG

1.97E+02

5.25E+04

-3.88E+05

1.12E+00

5.57E-02

DEG

2.45E+02

5.67E+04

-5.71E+05

1.12E+00

9.49E-02

TEG

2.78E+02

6.42E+04

-7.25E+05

1.13E+00

1.33E-01

TetraEG

3.08E+02

7.83E+04

-8.82E+05

1.12E+00

1.73E-01

143 Meanwhile, due to limited sources and information on time for TEGBE and TetraEGBE properties, the Cp values of these components are determined by its molecular formula by using Kopp‟s rule that were sourced from Third Edition Richard M. Selder & Ronald W.Rousseau published by John Wiley & Sons, inc. Kopp‟s rule is a simple empirical method for estimating the heat capacity of a liquid at or near 20 oC. According to this rule, Cp for a molecular compound is the sum contribution for each element in the compound. Thus, the heat capacities of triethylene glycol butyl ether (TEGBE) and tetraethylene glycol butyl ether (TetraEGBE) are as following: Table 7. 3: Atomic Capacities for Kopp’s Rule Element

Liquids [J/(g-atom.oC)]

C

12

H

18

O

25

For TEGBE, the molecular formula is C10H22O4. So the value of Cp, = (10 x 12) + (22 x 18) + (4 x 25) = 616 J/mol.0C For TetraEGBE, the molecular formula is C12H26O5. So the value of Cp, = (12 x 12) + (26 x 18) + (5 x 25) = 737 J/mol.0C Table 7.4: Cp values for TEGBE and TetraEGBE Component

Cp (J/mol.oC)

TEGBE

616

TetraEGBE

737

144 7.1

ENERGY BALANCE FOR HEATER

Figure 7.1: Diagram of Heater

Table 7.5: Temperatures and Pressures involved at the Heater

7.1.1

Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

111.4oC or 384.55 K

Temperature Outlet, Tout

120oC or 393.15 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

130 kpa

Pressure Outlet, Pout

4000 kpa

Inlet of Heater (stream 5):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.6: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 5 of heater n (kmol/hr) Water

∆H (J/mol)

Q (kJ/hr)

136.52

5

-2.37 x 10

-3.24 x 107

193

-1.92 x 104

-3.71 x 106

Ethylene Oxide

EGBE

5.8814

417616.3919

-2456169

Butanol TOTAL

4783

257162.0512

-1.23 x 109 -1.27 x 109

145 7.1.2

Outlet of Heater (stream 6):

Table 7.7: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 6 of heater

Water

n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

136.52

-2.37 x 105

-3.23 x 107

193

-1.84 x 104

-3.54 x 106

Ethylene Oxide

EGBE Butanol

5.8814 4783

414780.6894

-2439491.1 5

-2.12 x 10

TOTAL

By energy balance: ΣQ (outlet) - ΣQ (inlet)

Q

=

=

-1.27 x 109 – (-1.05 x 109)

=

-2.2 x 108 kJ/hr (heat been supplied to the system)

-1.013 x 109 -1.05 x 109

146 1. Sample calculations are as follows: The values of ΔH are calculated by using this formula: a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For Ethylene Oxide at Inlet of Heater (stream 5), ∆H

=

∆Hf + (V x ∆P) +

(-5.26E4) + [(2.90E-2) x (130-101.325)] + [((8.88E1) x (1.09E1-25)) + 2.57E4] + [(8.88E1) x (111.4-1.09E1)] =

-1.92E4 J/mol

+

147 3. For Ethylene Oxide at Outlet of Heater (stream 6), ∆H

=

∆Hf + (V x ∆P) +

+

(-5.26E4) + [(2.90E-2) x (4000-101.325)] + [((8.88E1) x (1.09E1-25)) + 2.57E4] + [(8.88E1) x (120-1.09E1)] =

-1.84E4 J/mol 4. Enthalpy, Q of Ethylene Oxide at Inlet of Heater (stream 5), Q

=

ΔH (J/mol) x

=

-1.92E4 x 193

=

-3.71E6 kJ/hr

(kmol/hr)

5. Enthalpy, Q of Ethylene Oxide at Outlet of Heater (stream 6), Q

=

ΔH (J/mol) x

=

-1.84E4 x 193

=

-3.54E6 kJ/hr

(kmol/hr)

148 7.2

Conversion Reactor

Figure 7.2: Diagram of Conversion Reactor

Table 7.8: Temperatures and Pressures involved at the Conversion Reactor Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

120oC or 393.15 K

Temperature Outlet, Tout

137.1oC or 410.25 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

4000 kpa

Pressure Outlet, Pout

3980 kpa

149 7.2.1

Inlet of conversion reactor (stream 6):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.9: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 6 of conversion reactor n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

136.52

5

-2.37 x 10

-3.23 x 107

193

-1.84 x 104

-3.54 x 106

EGBE

5.8814

-414780.6894 -2439491.1

Butanol

4783

-2.12 x 105

Water Ethylene Oxide

-1.05 x 109

TOTAL

7.2.2

-1.013 x 109

Outlet of conversion reactor (stream 8):

Table 7.10: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 8 of conversion reactors n (kmol/hr) B

∆H (J/mol) 5

Q (kJ/hr)

Water

136.52

-2.35 x 10

-3.21 x 107

DEGBE

29.433

-5.65 x 105

-1.66 x 107

EGBE

112.03

-410156.0575

-45949783.12

Butanol

117.81

-2.08 x 105

-2.45 x 107

TEGBE

8.685

-632850.228

-5.50 x 106

0.4825

-619780.7991

-299044.2356

TetraE GBE TOTAL By energy balance: ΣQ (outlet) - ΣQ (inlet)

Q

=

=

-1.05 x 109 – (-1.25 x 108)

=

-9.25 x 108 kJ/hr (heat been supplied to the system)

-1.25 x 108

150

1. Sample calculations are as follows: The values of ΔH are calculated by using this formula:

a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, ∆Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For EGBE at Inlet of Conversion Reactor (stream 6), ∆H

=

∆Hf + (V x ∆P) +

=

(-4.41E5) + [(1.31E-1) x (4000-101.325)] + [(2.71E2) x (120-25]

=

-414780.6894 J/mol

3. For EGBE at Outlet of Conversion Reactor (stream 8), ∆H

=

∆Hf + (V x ∆P) +

=

(-4.41E5) + [(1.31E-1) x (3980-101.325)] + [(2.71E2) x (137.1-25]

=

-410156.0575 J/mol

151 4. Enthalpy, Q of EGBE at Inlet of Conversion Reactor (stream 6), Q

=

ΔH (J/mol) x

=

-414780.6894 x 5.8814

=

-2.44E6 kJ/hr

(kmol/hr)

5. Enthalpy, Q of EGBE at Outlet of Conversion Reactor (stream 8), Q

=

ΔH (J/mol) x

=

-410156.0575 x 112.03

=

-4.59E7 kJ/hr

(kmol/hr)

152 7.3

Distillation Column 1

Figure 7.3: Distillation Column

Table 7.11: Temperatures and pressures involved at the Distillation Column 1 Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

137.1oC or 410.25 K

Temperature Outlet, Tout1

121.8oC or 394.95 K

Temperature Outlet, Tout2

195.3 oC or 468.45 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

3980 kpa

Pressure Outlet, Pout1

130 kpa

Pressure Outlet, Pout2

150 kpa

153 7.3.1

Inlet of Distillation Column 1 (stream 8):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.12: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 8 of distillation column 1

.

n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

Water

136.52

-2.35 x 105

-3.21 x 107

DEGBE

29.433

-5.65 x 105

-1.66 x 107

EGBE

112.03

-410156.0575

-45949783.12

Butanol

117.81

-2.08 x 105

-2.45 x 107

TEGBE

8.685

-632850.228

-5.50 x 106

TetraEGBE

0.4825

-619780.7991

-299044.2356 -1.25 x 108

TOTAL

7.3.2

Outlet of Distillation Column 1 (stream 9):

Table 7.13: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 9 of distillation column 1 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

Water

136.52

-2.37 x 105

-3.23 x 107

EGBE

5.6087

-414802.1519

-2326500.8

Butanol TOTAL

4638.3

5

-2.12 x 10

-9.82 x 108 -1.02 x 109

154 7.3.3

Outlet of Distillation Column 1 (stream 10):

Table 7.14: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 10 of distillation column 1 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

EGBE

106.42

-3.49 x 105

-3.71 x 107

DEGBE

29.433

-545383.6659

-16052277

TEGBE

8.685

-595085.0476

-5168313.6

TetraEGBE

0.4825

-574476.6554

-277184.99

Butanol

2

2.90 x 10

5

-1.97 x 10

TOTAL

By energy balance: Q=

ΣQ (outlet) - ΣQ (inlet)

=

(-1.02 x 109 + (-5.86 x 107)) – (-1.25 x 108)

=

-9.54 x 108 kJ/hr (heat been supplied to the system)

-5.71 x 103 -5.86 x 107

155 1. Sample calculations are as follows: The values of ΔH are calculated by using this formula:

a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, ∆Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For Butanol at Inlet of Distillation Column 1 (stream 8), ∆H

=

∆Hf + (V x ∆P) +

=

(-2.75E5) + [(9.14E-2) x (3980-101.325)] + [((2.05E2) x

+

(1.18E2-25)) + 4.32E4] + [(2.05E2) x (137.1-1.18E2)] =

-2.08E5 J/mol

3. For Butanol at Outlet of Distillation Column 1 (stream 9), ∆H

=

∆Hf + (V x ∆P) +

=

(-2.75E5) + [(9.14E-2) x (130-101.325)] + [((2.05E2) x

+

(1.18E2-25)) + 4.32E4] + [(2.05E2) x (121.8-1.18E2)] =

-2.12E5 J/mol

4. For Butanol at Outlet of Distillation Column 1 (stream 10), ∆H

=

∆Hf + (V x ∆P) +

=

(-2.75E5) + [(9.14E-2) x (150-101.325)] + [((2.05E2) x

+

(1.18E2-25)) + 4.32E4] + [(2.05E2) x (195.3-1.18E2)] =

-1.97E5 J/mol

156 5. Enthalpy, Q of Butanol at Inlet of Distillation Column 1 (stream 8), Q

=

ΔH (J/mol) x

(kmol/hr)

5

=

-2.08E x 117.81

=

-2.45E7 kJ/hr

6. Enthalpy, Q of Butanol at Outlet of Distillation Column 1 (stream 9), Q

=

ΔH (J/mol) x

(kmol/hr)

5

=

-2.12E x 4638.3

=

-9.82E8 kJ/hr

7. Enthalpy, Q of Butanol at Outlet of Distillation Column 1 (stream 9), Q

=

ΔH (J/mol) x

=

-1.97E5 x (2.90 x 102)

=

-5.71E3 kJ/hr

(kmol/hr)

157 7.4

Distillation Column 2

Figure 7.4: Distillation Column

Table 7.15: Temperatures and pressures involved at the distillation column 2 Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

195.3 oC or 468.45 K

Temperature Outlet, Tout1

101.4oC or 374.55 K

Temperature Outlet, Tout2

172.1 oC or 445.25 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

150 kpa

Pressure Outlet, Pout1

9 kpa

Pressure Outlet, Pout2

15 kpa

158 7.4.1

Inlet of Distillation Column 2 (stream 10):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.16: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 10 of distillation column 2 n (kmol/hr)

∆H (J/mol) 5

Q (kJ/hr)

EGBE

106.42

-3.49 x 10

-3.71 x 107

DEGBE

29.433

-545383.6659

-16052277

TEGBE

8.685

-595085.0476

-5168313.6

TetraEGBE

0.4825

-574476.6554

-277184.99

Butanol

2.90 x 102

-1.97 x 105

-5.71 x 103 -5.86 x 107

TOTAL

7.4.2

Outlet of Distillation Column 2 (stream 11):

Table 7.17: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 11 of distillation column 2

EGBE

n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

106.42

-420314.0279

-44729818.9

2.55 x 10-2

-578794.3233

-1.48 x 104

2.90 x 10-2

-259208.9339

-7.52 x 103

DEGB E Butan ol TOTA L

-4.48 x 107

159 7.4.3

Outlet of distillation column 2 (stream 12):

Table 7.18: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 12 of distillation column 2 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

DEGBE

29.407

-553633.9193

-16280713

TEGBE

8.685

-609368.3948

-5292364.5

TetraEGBE

0.4825

-591565.5843

-285430.39

TOTAL

-21858508

By energy balance: Q

=

ΣQ (outlet) - ΣQ (inlet)

=

(-21858508 + (-4.48 x 107)) – (-5.86 x 107)

=

-8.06 x 106 kJ/hr (heat been supplied to the system)

160 1. Sample calculations are as follows: The values of ΔH are calculated by using this formula: a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, ∆Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For DEGBE at Inlet of Distillation Column 2 (stream 10), ∆H

=

∆Hf + (V x ∆P) +

=

(-6.06E5) + [(1.70E-1) x (150-101.325)] + [(3.56E2) x (195.3-25]

=

-545383.6659 J/mol

3. For DEGBE at Outlet of Distillation Column 2 (stream 11), ∆H

=

∆Hf + (V x ∆P) +

=

(-6.06E5) + [(1.70E-1) x (101.325-9)] + [(3.56E2) x (101.4-25]

=

-578794.3233 J/mol

4. For DEGBE at Outlet of Distillation Column 2 (stream 12), ∆H

=

∆Hf + (V x ∆P) +

=

(-6.06E5) + [(1.70E-1) x (101.325-15)] + [(3.56E2) x (172.1-25]

=

-553633.9193 J/mol

161 5. Enthalpy, Q of DEGBE at Inlet of Distillation Column 2 (stream 10), Q

=

ΔH (J/mol) x

=

-545383.6659 x 29.433

=

-16052277kJ/hr

(kmol/hr)

6. Enthalpy, Q of DEGBE at Outlet of Distillation Column 2 (stream 11), Q

=

ΔH (J/mol) x

=

-578794.3233 x (2.55 x 10-2)

=

-1.48 x 104 kJ/hr

(kmol/hr)

7. Enthalpy, Q of DEGBE at Outlet of Distillation Column 2 (stream 12), Q

7.5

=

ΔH (J/mol) x

=

-553633.9193 x 29.407

=

-16280713 kJ/hr

(kmol/hr)

Distillation Column 3

Figure 7.5: Distillation Column

162 Table 7.19: Temperatures and pressures involved at the distillation column 3

7.5.1

Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

172.1 oC or 445.25 K

Temperature Outlet, Tout1

115.5oC or 388.65 K

Temperature Outlet, Tout2

223.6 oC or 496.75 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

15 kpa

Pressure Outlet, Pout1

1.9 kpa

Pressure Outlet, Pout2

15 kpa

Inlet of Distillation Column 3 (stream 12):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.20: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 12 of distillation column 3 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

DEGBE

29.407

-553633.9193

-16280713

TEGBE

8.685

-609368.3948

-5292364.5

TetraEGBE

0.4825

-591565.5843

-285430.39

TOTAL

7.5.2

-21858508

Outlet of Distillation Column 3 (stream 13):

Table 7.21: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 13 of distillation column 3 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

DEGBE

29.406

-573775.0684

-16872430

TEGBE

2.29 x 10-2

-644231.2625

-1.48 x 104

EGBE

3.86 x 10-4

-416497.6349

-1.61 x 102

TOTAL

-1.69 x 107

163 7.5.3

Outlet of Distillation Column 3 (stream 14):

Table 7.22: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 14 of distillation column 3 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

DEGBE

1.18 x 10-3

-4.81 x 105

-5.66 x 102

TEGBE

8.6621

-577644.3948

-5003613.512

TetraEGBE

0.48248

-553610.0843

-267105.7935 -5.27 x 106

TOTAL

By energy balance: ΣQ (outlet) - ΣQ (inlet)

Q

=

=

((-1.69 x 107) + (-5.27 x 106)) - (-21858508)

=

-3.11 x 105 kJ/hr (heat been supplied to the system)

1. Sample calculations are as follows: The values of ΔH are calculated by using this formula: a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, ∆Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For TEGBE at Inlet of Distillation Column 3 (stream 12), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.09E-1) x (101.325-15)] + [(6.16E2) x (172.1-25]

164 =

-609368.3948 J/mol

3. For TEGBE at Outlet of Distillation Column 3 (stream 13), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.09E-1) x (101.325-1.9)] + [(6.16E2) x (115.5-25]

=

-644231.2625 J/mol

4. For TEGBE at Outlet of Distillation Column 3 (stream 14), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.09E-1) x (101.325-15)] + [(6.16E2) x (223.6 -25]

=

-577644.3948 J/mol

5. Enthalpy, Q of TEGBE at Inlet of Distillation Column 3 (stream 12), Q

=

ΔH (J/mol) x

=

-609368.3948 x 8.685

=

-5292364.5 kJ/hr

(kmol/hr)

6. Enthalpy, Q of TEGBE at Outlet of Distillation Column 3 (stream 13), Q

=

ΔH (J/mol) x

=

-644231.2625 x (2.29 x 10-2)

=

-1.48 x 104kJ/hr

(kmol/hr)

7. Enthalpy, Q of TEGBE at Outlet of Distillation Column 3 (stream 14), Q

=

ΔH (J/mol) x

=

-577644.3948 x 8.6621

=

-5003613.512 kJ/hr

(kmol/hr)

165 7.6

Distillation Column 4

Figure 7.6: Distillation Column

Table 7.23: Temperatures and pressures involved at the distillation column 4 Reference Temperature, TR

25oC or 298 K

Temperature Inlet, Tin

223.6 oC or 496.75 K

Temperature Outlet, Tout1

150.2oC or 423.35 K

Temperature Outlet, Tout2

158.7 oC or 431.85 K

Reference Pressure, PR

101.325 kpa

Pressure Inlet, Pin

15 kpa

Pressure Outlet, Pout1

0.55 kpa

Pressure Outlet, Pout2

0.65 kpa

166 7.6.1

Inlet of Distillation Column 4 (stream 14):

From previous mass balance, the molar flow rate, Total enthalpy, ∑Q = ∑ΔH x

(kmol/hr) values are obtained.

(kmol/hr)

Table 7.24: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the inlet of stream 14 of distillation column 4 n (kmol/hr)

∆H (J/mol)

-3

5

Q (kJ/hr)

DEGBE

1.18 x 10

-4.81 x 10

-5.66 x 102

TEGBE

8.6621

-577644.3948

-5003613.512

TetraEGBE

0.48248

-553610.0843

-267105.7935 -5.27 x 106

TOTAL

7.6.2

Outlet of Distillation Column 4 (stream 15):

Table 7.25: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 15 of distillation column 4 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

DEGBE

1.18 x 10-3

-561425.4561

-6.60 x 102

TEGBE

8.6612

-622855.7809

-5394678.5

TetraEGBE

0.47755

-607702.2493

-290208.21 -5.69 x 106

TOTAL

7.6.3

Outlet of Distillation Column 4 (stream 16):

Table 7.26: shows the molar flow rate, n, delta enthalpy, ∆H and enthalpy, Q at the outlet of stream 16 of distillation column 4 n (kmol/hr)

∆H (J/mol)

Q (kJ/hr)

TEGBE

8.64 x 10-4

-617619.8018

-5.34 x 102

TetraEGBE

4.92 x 10-3

-601437.7744

-2.96 x 103

TOTAL

-3.49 x 103

167 By energy balance: ΣQ (outlet) - ΣQ (inlet)

Q

=

=

((-5.69 x 106) + (-3.49 x 103)) - (-5.27 x 106)

=

-4.2 x 105 kJ/hr (heat been supplied to the system)

1. Sample calculations are as follows: The values of ΔH are calculated by using this formula: a. Cp = aT² + (b/2) T² + (c/3) T³ + (d/4) T4 b. Cp = Cp (only applied for TEGBE and TetraEGBE) c. ΔH (J/mol) = ∆Hf + (V x ∆P) + Where, ∆Hf

=

Heat of Formation

V

=

Specific Volume

Cp

=

Heat Capacity

∆P

=

Pressure Drop

∆Hv

=

Heat of Vaporization

TR

=

Reference Temperature

Tb

=

Boiling Temperature

Ts

=

Source Temperature

+

2. For TetraEGBE at Inlet of Distillation Column 4 (stream 14), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.52E-1) x (101.325-15)] + [(7.37E2) x (223.6-25]

=

-553610.0843 J/mol

168 3. For TetraEGBE at Outlet of Distillation Column 4 (stream 15), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.52E-1) x (101.325-0.55)] + [(7.37E2) x (150.2-25]

=

-607702.2493 J/mol

4. For TetraEGBE at Outlet of Distillation Column 4 (stream 16), ∆H

=

∆Hf + (V x ∆P) +

=

(-7.00E5) + [(2.52E-1) x (101.325-0.65)] + [(7.37E2) x (158.7-25]

=

-601437.7744 J/mol

5. Enthalpy, Q of TetraEGBE at Inlet of Distillation Column 4 (stream 14), Q

=

ΔH (J/mol) x

=

-553610.0843 x 0.48248

=

-267195.7935 kJ/hr

(kmol/hr)

6. Enthalpy, Q of TetraEGBE at Outlet of Distillation Column 4 (stream 15), Q

=

ΔH (J/mol) x

=

-607702.2493 x 0.47755

=

-290208.21kJ/hr

(kmol/hr)

7. Enthalpy, Q of TetraEGBE at Outlet of Distillation Column 4 (stream 16), Q

=

ΔH (J/mol) x

=

-601437.7744 x (4.92 x 10-3)

=

-2.96 x 103kJ/hr

(kmol/hr)

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