oleochemical dkk
DESCRIPTION
Basic OleochemicalTRANSCRIPT
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GLOBAL CONSUMPTION OF OILS AND FATS
OLEOCHEMICAL
OLEOCHEMICAL
OLEOCHEMICAL Chemical derives from natural oils and fats as opposed to chemical derived from petrochemical
feedstock
BASIC OLEOCHEMICAL OLEOCHEMICAL DERIVATIVES
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• Most common – biodiesel production
• Production of detergents (lauric acid used to produce sodium lauryl sulfate, the main ingredient in many personal care products)
• Production of lubricants, green solvents, bioplastics, cosmetics
APPLICATION OF OLEOCHEMICAL
• Started in the early 1979 (10,000 tonnes of fatty acids and glycerol)
• Palm oil and its deivatives and palm kernel oil as feedstock
• Local and several joint-venture companies with multinationals
MALAYSIAN OLEOCHEMICAL INDUSTRY
• Malaysia is the leading producer and exporter of basic oleochemicals in the world
MALAYSIA’S PALM OIL INDUSTRY
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MALAYSIAN PALM OIL INDUSTRY EXPORT (2011)
- derived from renewable resources, as compared to petrochemicals which are obtained from exhaustible or non-renewable petroleum
- more readily biodegradable and hence do not pose a threat to the environment
- products derived from petroleum sources use more energy and cause higher emissions of pollutants such as NO2, SO2, CO & hydrocarbons
OLEOCHEMICAL VS PETROCHEMICAL
- Costs of crude oil and fuel remain high
- Continued price increase in petrochemical-derived ingredients
OLEOCHEMICAL - AN ALTERNATIVE FEEDSTOCK
- Renewable raw materials
- Expanding global oilseed production
- Government subsidies and incentives
- Increasing regulation for synthetic/petrochemical-based ingredients
- Increased in R & D for vegetable oil-based industrial products and fuel
- Increased interest from traditional petro-based manufacturers
- Growing importance of biotechnology
- Consumer preference for ‘naturals’
- Growing trend in green chemistry
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WORLDWIDE SOURCES OF RAW MATERIALS FOR OLEOCHEMICALS
RAW MATERIALS FOR OLEOCHEMICAL
• Prior to 1985, tallow was an important raw material for the oleochemical industry
• Main feedstock: tallow and coconut oil
• due to BSE, tallow has been replaced in most of the personal care by PO
RAW MATERIALS FOR OLEOCHEMICAL
• Coconut oil, the only other oil with short- and medium- chain FA, has not been growing in the last years, and has therefore lost ground to palm kernel oil
source: U. R. Sahasranamam
Mill
ion
MT
• stagnant global availability of tallow & coconut oil, greater availability of palm oil & palm kernel oil
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COCONUT OIL VS PALM KERNEL OIL
PALM KERNEL OIL
• 2006 – 1.99 million tonnes of PO & PKO (60% PKO and 5% PO) processed into oleochemicals
• PKO extremely important due to its short (C8-C10) and medium-chain (C12-C14) FA whereas PO its long chain (C16-C18) FA
• PO & PKO covering the total needs of the oleochemical industry with the exception of high-erucic rapeseed oil (C20 and C22 )
Source : Wolfgang Rupilius, Salmiah Ahmad
ADVANTAGES OF PALM KERNEL OIL
come from the same source, unlike coconut oil and tallow
constant supply of raw materials
PO & PKO advantages over tallow & coconut oils:
palm based oleochemicals derived from vegetable sources, unlike tallow which is animal-based
palm based oleochemicals enjoy the versatility of various palm-based derivatives
palm-based products are more economical
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BASIC OLEOCHEMICAL
• Malaysia is one of the world's leading basic oleochemicals producers and net exporters
BASIC & INTERMEDIATES OLEOCHEMICALS’ USES
BASIC OLEOCHEMICAL
source: Dr Salmiah Ahmad
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BASIC OLEOCHEMICALS, OLEODERIVATIVES & END-PRODUCTS
BASIC OLEOCHEMICALS
FATTY-ACID
Direct uses As derivatives Intermediate chemicals for
• Rubber processing • Candles • Cosmetic products
• Medium chain triglycerides(MCT) • Soap • Production of mettalic soap
• Fatty alcohols • Fatty amines • Fatty esters
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FATTY-ACIDS
• gate way to other oleochemicals
Palm oil/Palm Kernel oil
(Fat Splitting) hydrolisis
Crude fatty acid
Separation -Distillation
-Hydrogenation -Fractional distillation
-distilled Fatty acid -saturated fatty acid
-unsaturated fatty acid -fractionated fatty acid
FATTY-ACIDS
• palmitic acid or stearic acid obtained from both PO & PKO via hydrolytic splitting, fractional distillation and hydrogenation
• shorter chain fatty acids (C14 or lower) esp. lauric acid are from coconut or palm kernel oil (only commercially available lauric oils)
• a reversible reaction
FAT-SPLITTING/HYDROLYSIS
• in stages (tri to di to mono)
• initial stage : reaction proceeds slowly (low solubility of the water in the oil phase)
• second stage : reaction proceeds fairly rapidly (greater solubility of water in the fatty acids)
• final stage : diminishing reaction rate (reach equilibrium)
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FAT-SPLITTING
• increasing temperature & pressure accelerates the reaction (increased solubility of the water in the oil phase & higher activation energy)
• glycerine byproduct must be withdrawn continuously to force the reaction to completion
• small amounts of mineral acids (sulfuric acid) or certain metal oxides (zinc or magnesium oxide) accelerates the splitting reaction
SPLITTING COLUMNS The deaerated fat is introduced by means
of a sparge ring, around 1 m from the boDom with a high-‐pressure pump.
Water is introduced near the top at a raIo of 40–50% of
the weight of the fat.
The high spliMng temperature (250–
260⁰C) and a pressure (50-‐55 bar) ensures
adequate dissoluIon of the water phase into the
fat
Crude FaDy acid Sweetwater(glycerol)
CONTINUOUS HIGH PRESSURE FAT-SPLITTING PROCESS
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• production involves pretreatment to remove phosphatides, heavy metals & solid matters
FATTY ACIDS
• pretreated oils are then split using demineralized water at 250 – 255oC and a pressure of 50-55 bar into fatty acids & sweetwater (15% glycerol)
• crude FA produced are then purified to remove colour bodies, partial glycerides, unsaponifiable matter, polymerized FA and free glycerol by simple distillation or separated into component homologues by fractional distillation
• hydrogenation is carried out if high quality saturated acids are required
• separation of palmitic & stearic acids, a fractionator with a single column of 20 trays may be used
• separation of PKO into C8/C10, C12, C14,C16/C18 uses multi-columns
FATTY METHYL ESTERS
• development of biodiesel (clean burning with no sulfur dioxide emission) methyl esters have become the fastest growing oleochemicals
FATTY METHYL ESTERS
• usually manufactured directly from oils via methanolysis with alkaline catalysts (eg. Sodium methylate)
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FATTY METHYL ESTER
GLOBAL BIODIESEL PRODUCTION
• fatty acid methyl esters (FAME) have increasingly replaced fatty acids as starting materials for many oleochemicals
FATTY ACID METHYL ESTER
1. production of methyl esters requires much lower reactor temperatures and pressures than the splitting of fats and oils to obtain fatty acids
2. methyl ester are noncorrosive & are produced at lower operating temperature & pressure (processed in carbon steel equipment); FA are corrosive (heavy-duty stainless steel equipment)
3. transesterification is a dry reaction & yelds conc. glycerine, while fat splitting produces glycerine water which has more than 80% water (uses more energy to recover)
4. esters are more easily distilled because of their lower boiling points & are more heat stable than the corresponding FA
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MPOB PALM BIODIESEL PRODUCTION
• in Malaysia, fatty methyl esters are prepared via 2 routes:
TRANSESTERIFICATION
1. Transesterification (methanolysis) of triglycerides with methanol (most common method)
• alkaline catalysts are used with sodium methylate (most effective) although sodium hydroxide can also be used
• sequence of steps is triglyceride to diglyceride to monoglyceride with1 mole of methyl ester formed at each cleavage
ESTERIFICATION
2. Esterification of fatty acids with methanol (more cost intensive)
• reversible reaction thus, water must be removed to drive the reaction to the right and obtain a high-ester yield
• acid catalysts like sulfuric acid are employed
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FATTY ALCOHOLS
• one of the major basic oleochemicals enjoying a continuing growth rate (primary raw material for surfactants [80%])
FATTY ALCOHOLS - PROCESS
• direct hydrogenation of fatty acids
• “Natural” fatty alcohol:
• hydrogenaIon of faDy methyl esters
HIGH PRESSURE HYDROGENATION USING SUSPENSION PROCESS
• a two-step reaction:
• Lurgi method
• overcomes the damaging effects of the fatty acids on the copper-bearing analyst
• both reactions occur simultaneously in the same reactor
• fatty alcohol recirculated, more than 250 times the fatty acid feed, effectively dilutes the feed, hence rapid and complete esterification
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FATTY ALCOHOLS
FATTY ALCOHOL • crude fatty alcohol undergoes fractionation to produce different cuts of alcohol
FATTY AMINES
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FATTY AMINES
• bases for the manufacture of quaternary ammonium compounds used as fabric softeners and biocides
• most important nitrogen derivatives of fatty acids
• produced by the reaction of fatty acids with ammonia and hydrogen
• main raw material is the fatty nitrile derived from the reaction of fatty acid with ammonia
• fatty amine oxides are mild to the skin with good cleaning and foaming properties and find application as a shampoo ingredient
• catalytic hydrogenation of the nitrile produces the amines
FATTY AMINES • available as primary, secondary, and tertiary amine, depending on the number of the alkyl groups attached to the nitrogen atom
• which amines are produced depends on the reaction conditions (NH3 pressure & temperature) & catalyst choice (Raney Ni or supported Ni powders)
CHEMISTRY OF FATTY AMINES PRODUCTION
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GLYCEROL
• chemical formula, C3H803
• also known as glycerin/glycerine (commercial grades)
• by-product of fatty acid, methyl esters & biodiesel and fatty alcohol production
• used in cosmetics, pharmaceuticals, explosives, food & tobacco
• supply increasing due to increasing production of biodiesel & use of oil & fats as industrial feedstock
• colourless, odorless, viscous & non-liquid, have slight sweet taste
GLYCEROL
GLYCEROL PRODUCTION
Glycerol ProducIon
Trans-‐esterificaIon
Hydrolysis SaponificaIon
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SAPONIFICATION
• also known as soap formation
• oil/fat reacts with caustic soda to form soap and soap lye
• soap lye formed contains 4 – 20% glycerol (also known as sweetwater)
SPLITTING
• also known as hydrolysis
• under pressure and at high temperature to produce fatty acids and sweetwater
• sweetwater contains 10 – 20% glycerol
TRANSESTERIFICATION
• oil reacts with methanol in the presence of catalyst to yield methyl esters
• glycerine concentration in excess of 90% can be obtained as this is basically a dry reaction
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GLYCEROL PURIFICATION
• sweetwater or glycerine obtained from the three processes contains impurities and must undergo further purification and concentration
DISTILLING & REFINING GLYCEROL
• distilled under a high vacuum of 660–1330 Pa absolute
• condensed glycerine (99.5%, purity) undergoes steam deodorization by in a deodorizer under high vacuum
• bleached with activated carbon and filtered to yield pharmaceutical-grade glycerine with a purity of 99%
• Lower quality distillate is collected and sold separately as technical-grade glycerine