Palm Oil: Going Beyond Basic Oleochemicals

Transcription

1 Palm Oil: Going Beyond Basic Oleochemicals Venue: Bucharest, Rumania Date: 18 th September, 2012 By: S.K. Yeong, Hazimah A.H. and Y.M. Choo MALAYSIAN PALM OIL BOARD

2 What are OLEOCHEMICALS? Chemicals derived from natural oils/fats - could be of animal, marine or vegetable oil sources Derived from breaking the oils/fats into corresponding constituents, i.e. fatty acids, glycerol, fatty esters, etc. Normal process involves hydrolysis or transesterification 2

3 12.9 mil tonnes 41.7 mil tonnes SUNFLOWER 50.2 mil tonnes RAPESEED 23.5 mil tonnes SOYBEAN Global production oils and fats in Source: Oil World Annual, Oil World Weekly and Malaysian Oil Palm Statistics PALM 3

4 Palm Oil Mesocarp Kernel Malaysia 2011: Production of CPO = 18.9 mil tonnes Production of CPKO = 2.14 mil tonnes 80-85% for food applications 15-20% for non-food applications

5 Palm Oil Chemistry CH 2 OCOR 1 CH 2 OH R 1 COOH HC OCOR 2 3 H2O HC OH R 2 COOH CH 2 OCOR 3 CH 2 OH R 3 COOH Triglyceride Water Glycerol Fatty acids R 1, R 2 and R 3 vary in chain length and degree of unsaturation 5

6 Composition of Oleochemicals Depends on Starting Raw Materials R, R, R Palm oil Palm stearin Tallow Coconut oil Palm kernel oil C C C C C C % 48.8% C C16: C18: C18: C18: OTHERS

7 Basic Oleochemicals Basic: Fatty acids Fatty methyl esters Fatty alcohols Fatty amines Glycerine Derivatives: basic oleochemicals subjected to further reactions 7

8 Production of Oleochemicals Hydrolysis Transesterification Amination Hydrogenation Amination Hydrogenation 8

9 Oleochemicals Industry in Malaysia Started with one plant in 1980 Currently in operation 17 plants - total production capacities 2.6 million tonnes. Major feedstock - processed PO, PS and PKO 9

10 Malaysian Oleochemicals: Export Volume and Value Volume, Mil Mt 6.00 Value, RM Bil Volume, mil tonne Value, bil RM 10

11 Export Volume of Basic Oleochemicals 1000 Volume, x10 3 tonne Fatty acid Fatty alcohol Methyl ester Glycerine 11

12 Major Export Destinations Rest of World, 39.11% European Union, 22.59% China, 14.49% EU China Japan U.S.A. India R.O.W. India, 5.51% U.S.A., 8.52% Japan, 9.76% 12

13 Beyond Basic Value Consumer Products High Formulation (Semi Finished) Derivatives (Intermediate Chemicals) Basic Oleochemicals Refined Oil Palm Fruit Low

14 Application of Oleochemicals Surfactant Washing and cleaning products Personal care products 14

15 Surfactant Surface active agent, a chemical that stabilises mixtures of oil and water by reducing the surface tension at the interface between the oil and water molecules Function - detergent, wetting agents, emulsifiers, conditioning agents, solubilisers. Hydrophillic head (charged molecules dissolves in water) and hydrophobic tail (long hydrocarbon chain derived from palm) 15

16 C12-C14 fatty acids for foams/lathers (from palm kernel oil) C16-C18 fatty acids for cleaning purposes (from palm oil) 16

17 Soap Soap is still the major application in the non-food sector 3 major methods of production Saponification of oils/fats Neutralization of fatty acids Saponification of methyl ester 17

18 Soap from Oils and Fats (Saponification) RCH 2 COO-CH 2 RCH 2 COO-CH RCH 2 COO-CH 2 3NaOH 3 RCH 2 COO - Na + + CH 2 OHCHOHCH 2 OH Soap + USP glycerin Mixture of fresh PO/PKO are boiled with excess alkali Oils/fats converted to soap and soap lye. Brine is added for better separation The soap is dried, to produce soap. The soap lye is processed to USP grade glycerin 18

19 Soap from Fatty Acids (Splitting) RCH 2 COO-CH 2 RCH 2 COO-CH RCH 2 COO-CH 2 3 RCH 2 COOH Steam + CH 2 OHCHOHCH 2 OH Fatty acids USP glycerin In 80 s, oleochemicals industry developed in Malaysia Fresh PO or PKO are split to fatty acids and sweet water The fatty acids are either distilled, stripped or fractionated. The sweet water is processed to USP grade glycerin 19

20 Soap from Fatty Acids (Neutralisation) RCH 2 COOH NaOH Distilled, broad cut or fractionated fatty acids are neutralized to form soap. RCH 2 COO - Na + Soap 20

21 Soap Quality of soap noodles produced in Malaysia PO 80, 75, 70, 60 PKO 20, 25, 30, 40 H 2 O % TFM 79-83% FFA % GLY % Sesq. Present Titer o C

22 Soap Pilot Plant AMALGAMATOR 2. ROLL MILL 3. PLODDER 4. PNEUMATIC PRESS MOULD 4

23 Specialty Soap Specialty soaps - contain special additives for specific functionality (1-5%) Process similar to toilet soaps Categories of additives: emollients, humectant, moisturisers, occlusive agents, dermabrasive agents, medicaments, antiirritants, etc.

24 Transparent Soap Recently transparent soaps are very popular Palm-based fatty acid was used to replace tallow Process - neutralization of fatty acids Can be used for decoration and skin care Use as gifts 24

25 Typical Formulation of Transparent Bar Soap Ingredient Fatty acids NaOH Glycerol Sugar Alcohol EDTA Water Function Surfactant Neutralizer Humectant Humectant Solvent Sequestering agent or chelating agent Filler 25

26 1 Process of Making Transparent Bar Soap at Lab Scale 3 2 Neutralization of fatty acids Sugar, glycerol, alcohol, EDTA, water Soap 26

27 Colour Perfume 27

28 Mould 28

29 Performance Evaluation of Transparent Bar Soap Detergency test Foaming test Transparency value Hardness Ocular and dermal irritation test 29

30 Advantages of Palm-based Transparent Bar Soap Contains natural ingredient Low ph closer to ph of skin 30

31 Fatty Alcohols Most important market for fatty alcohols are mid-cut (C ) and long chain (C ) Derivatized - fatty alcohol ethoxylate (FAE), fatty alcohol ether sulphate (FAES), fatty alcohol sulphate (FAS). 31

32 Major application surfactants for household detergents For example dishwashing liquid, shampoo, shower bath, etc. 32

33 Methyl Ester Sulphonate (MES) MES is an anionic surfactant derived from oleochemicals. Therefore it is derived from renewable sources. It is used as active compound in cleaning products. Its can be used to replace linear alkyl benzene sulphonate (LAS), the most commonly used petrochemical based surfactant in detergent products. 33

34 CH 3 -(CH 2 ) n -CH-COOCH 3 SO 3- Na + (dissolves in water with the head group negatively charged = anionic surfactant) 34

35 MES Process METHYL ESTER Hydrogenation SATURATED METHYL ESTER (IODINE VALUE < 0.5) Sulphonation Digestion Bleaching Neutralisation Drying Methyl Ester Sulphonate (MES) 35

36 Methyl Ester Sulphonates (MES) Saturated methyl ester as feedstock PROPERTIES OF MES FROM PALM STEARIN Parameters Active (%) Disalt (%) Volatile (%) Methanol(%) H 2 O 2 (%) Colour (Klett) Guaranteed >85 <6 <2.5 <0.4 <0.1 <100 MPOB

37 Performance of MES Good washing performance in hard water and without phosphate Good hard water tolerance Good synergy with soap as additive Good solubility Soft and no skin irritaion Good biodegradability C12 C14 C16 C18 LAS AS C12 C14 C16 C18 LAS AS C12 C14 C16 C18 LAS AS 54ppm 270ppm LAS MES 37

38 Application of MES MES produced by MPOB has been successfully formulated into powder and liquid detergent Formulations is usually kept as a trade secret by individual producer 38

39 Fatty Amines Derivatives of Fatty acids and Fatty alcohol. Traditionally derived from reaction of fatty acids or fatty alcohols and ammonia or urea Classified as Primary, Secondary, Tertiary amines and Quaternary Ammonium Compounds. 39

40 Examples of Fatty Amines (chemical structures) H H H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C NH 2 H H H H H H H H H H H H H H H H hydrocarbon feedstock = R ammonia PRIMARY AMINES H CH 3 R CH 2 N R CH 2 N CH 3 Secondary amines Tertiary amines CH 3 40

41 Examples of Fatty Amines (Quaternary Ammonium Compounds or Quats) R R CH 2 N + CH 3 CH 3 Traditional dialkyl quats Cl - Yellow : hydrocarbon source Cyan: hydrophilic positive amine Cyan: hydrophilic negative counter ion Preferred chemical structure: Esterquats-more environmentally acceptable O HO CH 2 CH 2 + N H 3 C CH 2 CH 2 CH 2 CH 2 O O C C CH 2 CH 2 R R CH 3 SO 4 - O Quaternary triethanolamine ester or esterquats 41

42 Main Application of Fatty Amines Primary and secondary amines are used as precursor for tertiary amines Largest application of fatty amines were in textile industries though some may go into specialized industries such as floatation ores, bactericides and additives in plastic Awareness in environmental issues have changed the fatty amines industries significantly especially in household fabric care / softener

43 Why we Need to Use Fabric Softener in First Place? 1.Softening and long lasting fragrance on cotton fabric: e.g towel. 2.Prevent accumalation of static charges on silk materials 3.Prevent excessive wrinkle on fabric after laundry 43

44 Current Trend: Easily Biodegradable To reduce accumalation of cationic material that will retard the balance of ecosystem in the environment X 44

45 Fabric Softener from Palm Oil Palm Oil Fruits Palm Oil Palmityl O O H 3C N - CH 3SO 4 + Fabric Softener Stearyl Hydrophobic tail O O HO Positively charged hydrophilic head Quaternary triethanolamine ester or esterquats Fatty acid methyl ester or fatty acids 45

46 Cosmetic & Personal Care 46

47 Cosmetic and Personal Care Cosmetic and personal care are substances or preparation intended to placed on the external part of human body with the aim to cleaning them, perfuming them, changing their appearance and protecting them or keeping them in good condition.

48 COSMETICS WHITE COSMETICS LOTION CREAM COLOURED COSMETICS FOUNDATION LIPSTICK HAIR DYES BLUSHER EYE SHADOW COSMETICS AND PERSONAL CARE PERSONAL CARE HAIR SHAMPOO CONDITIONER SKIN SHOWER GEL SHOWER CREAM SHOWER FOAM SOAP FACE FACIAL CLEANSER TONER MOISTURISER ORAL TOOTH PASTE MOUTH WASH HYGIENE DEODORANT OTHERS 48

49 Emulsifier Emulsifier - a type of surfactant used to keep emulsion (immiscible fluids) well dispersed. Hydrophillic head (water loving) Lypophillic tail (oil loving) O/W Emulsion W/O Emulsion Oil 49

50 Importance of Emulsifier Oil Water Emulsifier 50

51 Oleochemicals in CPC products Function Class Examples Emollients Fatty acids Fatty alcohols Esters Triglycerides Humectant Polyol Glycerin Surfactants/ emulsifying agents Soaps Esters Ethers Anionic surfactants Stearic acid Cetyl/Stearyl/Cetearyl alcohols IPM, IPP PK glycerides, MCT Stearates, Myristates (Na, TEA) Glyceryl stearates, Sorbitan Stearates Ceteareth-2, 12, Steareth-2, 21 SLS, SLES Thickener Fatty alcohols Cetyl/ Stearyl/Cetearyl alcohols 51

52 Active Ingredients in Cosmetic Products Active ingredients Sunscreen Whitening agent Anti wrinkle Anti inflammatory Moisturising agent Anti acne Example 3,4-Benzophenon, zinc oxide, titanium dioxide Arbutin, Kojic acid Vitamin A (carotenoids) and E (tocopherol and tocotrienol) Tea tree oil Plant extract eg. cucumber extract Tea tree oil 52

53 Colour cosmetic, for example compact powder, liquid foundation, lipstick, etc.

54 Leave on or wash off products with vitamin E. Example, lotion, cream, shampoo, conditioner, etc.

55 Glycerol Glycerol is a polyol obtained from either hydrolysis or transesterification coproduct of the fatty acid, fatty alcohol and biodiesel industries CH 2 OHCHOHCH 2 OH mwt 92 Non toxic, widely used in food, cosmetic and pharmaceutical industries 55

56 Glycerol. Traditional Applications Many grades pharmacopia > 99.5% medical & food uses Solvent/drugs carrier cough mixture, antibiotics In food products as texture improver, eg. ice cream Transparency effect in soap Antifreeze when add to water lowers melting point of water 56

57 Hygroscopic useful as humectant in cosmetics, toothpaste, tobacco to prevent moisture loss on storage Combine with other polyols to produce polyurethane Convert to monoglyceride as emulsifier for margarine, bakery products Glycerol + HNO 3 nitroglycerine an explosive 57

58 Recent Applications Epichorohydrin - building blocks for elastromer, resin, etc. Propylene glycol - as humectant in cosmetic, toothpastes, food, tobacco products, carrier for fragrance. Polyglycerol - converted to polyglycerol esters mainly used as emulsifiers cosmetics and food. 58

59 Glycerol Derivatives Polyglycerol from Crude Glycerine A potential outlet for biodiesel glycerine Crude glycerol Crude polyglycerol Purified polyglycerol

60 Polyol and Polyurethane Polyol are compounds with multiple hydroxyl functional groups H-O-R-O-H Reacted with isocyanates to make polyurethane Two possible chemical process Alkoxylation polyether polyol Esterification polyester polyol

61 Natural Polyol Derived from vegetable oils by several different techniques. Types of vegetables oil: Castor oil, Soya bean oil, Canola oil, Peanut oil and Palm oil Castor oil has been used since the only natural occurring polyol Other are produced via chemical modifications

62 Polyol Polyol pilot plant

63 Formation of Polyurethane ISOCYANATE POLYOL GLYCEROL, DERIVATIVE OF TRIGLYCERIDES OR GLYCEROL POLYURETHANE

64 High Pressured PU Machine

65 Palm-based PU for Automotive Components PU products formulated palm-based polyol made from palm oil

66 Rigid PU

67 Ornamental products Islamic motives Ornamental products contemporary motives

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