New Syntheses with Oils and Fats as Renewable Feedstocks for the Chemical Industry

Transcription

1 New Syntheses with ils and Fats as Renewable Feedstocks for the Chemical Industry Green Chemistry: Development of Sustainable Processes Rostock,

2 - Introduction - leochemistry - C,C-Bond forming additions - New oil crops - New base chemicals - Conclusion

3 The twelve principles of green chemistry 7. A raw material of feedstock should be renewable rather than depleting wherever technically and economically practicable.

4 Agenda 21 Chapter 4 CHANGING CNSUMPTIN PATTERNS encouraging the environmentally sound and sustainable use of renewable natural resources.

5 Feedstocks of the Chemical Industry in Germany (1991) Natural gas 1,7 Mio. t 8% Renewables 1,8 Mio. t 8% Petroleum 18,4 Mio. t 82% Most products obtainable from renewable raw materials may at present not be able to compete with the products of the petrochemical industry, but this will change as oil Coal 0,5 Mio. t 2% becomes scarcer and oil prices rise. The German Chemical Society calls on governments to step up promotion of the necessary basic research and to create frame conditions that encourage the kind of private-sector research that would make sustainable substitute processes and products ready in good time. Position paper of the GDCh presented to the governments of the countries participating in the World Summit on Sustainable Development in Johannesburg, 2002.

6 Targets of Biobased Products in the USA 30% 25% Proportion of the total production in % 20% 15% 10% Energy Fuels rganic chemicals 5% 0% Jahr Vision for Bioenergy & Biobased Products in The United States, Biomass Research and Development Technical Advisory Comitee, ctober 2002,

7 Renewable Feedstocks of the Chemical Industry in Germany (2002) Fats and ils t 47% S tarch t 31% thers t 5% Sugar t 4% Cellulose t 13%

8 World Consumption of ils and Fats (2002, mil mt) Total Food Chemistry Feed 81 % 14 % 5 % World Consumption of Mineral il in 2002: approx mil mt

9 Raw Materials World Production of ils and Fats 2002 (120.3 mil mt) vegetable (approx. 80%) 29.7 animal (approx. 20 % declining) Soy Palm Rape Sunflower Tallow Butter Laurics ther Laurics: Coconut and palm kernel C 12

10 Distribution of Fatty Acids in Triglycerides glycerol backbone fatty acids Carbon Chain Material coconut oil palm kernel oil palm oil rape oil (old) rape oil (new) sunflower (old) 6 93 sunflower (new) soy oil 8 91 lard double bonds C

11 Chemical Conversion of Triglycerides: Splitting + 3 R H T [cat] H H H + R R R Triglyceride + water glycerol + fatty acids Triglyceride + methanol glycerol + fatty acid methyl ester

12 Fatty Alcohols Cu/Cr 2 3 R + H 2 H + RH C; 250 bar R Zn/Cr H 2 H + RH - production by continuous hydrogenation of esters - over 1 mil mt produced from renewable raw materials - main raw material for saturated alcohols: coconut and palm kernel oil - competing processes using petrochemical sources Ethylene: Ziegler, Alfol-Process lefins: Hydroformylation/Reduction - share of natural sources is rising

13 Alkyl Polyglycosides (APG) H + H H H H H H H H - nonionic surfactant - very good biodegradability - good skin compatability detergent for home care applications cosmetics t/a H H H H

14 leochemical Production Flow Scheme Raw Materials leochemicals Specialties oils & fats fatty acid methyl ester fatty acids fatty alcohols sulpho fatty acid esters guerbet alcohols alkyl chlorides fatty alcohol ethoxylates fatty alcohol sulfates technical esters alkyl polyglycosides conjugated fatty acids alkyl epoxyesters dimer acids fatty acids ethoxylates azelaic/pelargonic acids fatty acid esters glycerol triacetin partial glycerides

15 Unsaturated fatty acids 9 CH 6 CH 13 CH 12 9 CH H 9 CH 10 CH

16 Manganese(III)acetate initiated radical addition of acetic acid to methyl oleate CH 2 CH 9 CMe + CH 3 CH 43% Mn(Ac) 3 /KAc/HAc C 9 CMe +regioisomer J.. Metzger, U. Linker, Fat Sci. Technol. 1991, 93,

17 Copper initiated addition of methyl 2-iodopropanoate to methyl 10-undecenoate 10 CMe + CMe I + Cu - Mel C 86% No solvent! CMe [(cis)] : [(trans)] = 1.3 : 1 J.. Metzger, R. Mahler, G Francke, Liebigs Ann. 1997,

18 Mechanism of the copper initiated addition of activated iodoalkanes to alkenes I CH 2 C 2 Me + Cu - CuI R -MeI Me 2 C I R CH 2 C 2 Me R I CH 2 C 2 Me Me 2 C R R = alkyl, (CH 2 ) 8 CMe)

19 Synthesis of perfluoroalkyl branched octadecanoic acids 9 CMe + R F I yield % Cu / 130 C or Pb / Cu(Ac) 2, MeH, r.t. or SnCl 2 / AgAc, MeH, r.t. I 10 9 R F CMe 1. H 2, Pd / C 2. KH / H R F CH R F = C 4 F 9, C 6 F 13, C 8 F perfluoroalkyl isomer J.. Metzger, R. Mahler, A. Schmidt, Liebigs Ann. 1996,

20 Dimethylaluminum chloride induced addition of formaldehyde to petroselinic acid 7 6 H 73% 1. (CH 2 ) n, Me 2 AlCl, CH 2 Cl 2 2 h, r.t. 2. H H H 1 H 5 6 H 2 petroselinic acid : paraformaldehyde : Me 2 AlCl = 1: 2 : 2 [1] : [2] = 55 : 45 J.. Metzger, U. Biermann, Synthesis 1992,

21 AlCl 3 induced addition of formaldehyde to methyl oleate CMe + (CH 2 ) n 86% 1. AlCl 3, CH 2 Cl 2, 24 h, r.t. 2. H Cl 8 + Me [1] :[2] = 3 : 1 2 Cl regioisomers Me methyl oleate : paraformaldehyde : AlCl 3 = 2 : 4 : 1 J.. Metzger, U. Biermann, Bull. Soc. Chim. Belg. 1994, 103,

22 Mechanism of AlCl 3 induced Prins-type reaction H AlCl 3 + H 2 C = + AlCl 3 Cl 3 Al = CH 2 H- - AlCl 2 H Cl Cl Cl Al- H H 2 C Cl

23 AlCl 3 induced reaction of heptanal and methyl ricinoleate H 12 9 CMe + H 76% AlCl 3, CH 2 Cl 2 RT, 4 h Cl H 3 C 9

24 AlCl 3 induced tetrahydropyran formation CH 3 H R R H AlCl 2 C R Cl H H R - AlCl 2 H + C + AlCl 3 R R Cl R = (CH 2 ) 5 CH 3 ; R =(CH 2 ) 7 CCH 3

25 EtAlCl 2 induced acylations of oleic acid 9 CH + R Cl 40-58% 1. EtAlCl 2, CH 2 Cl 2, 24 h, r.t. 2. H 2 R 10 H + regioisomer R = Me, nc 6 H 13, nc 15 H 31, cc 3 H 5, Ph,, S Me HC CH J.. Metzger, U. Biermann, Liebigs Ann. 1993,

26 Alkyl branched fatty acids H

27 Characteristics of alkyl branched fatty compounds good spreadability good solubility in cosmetic formulations good emolliency low viscosity low pour points good oxidative and hydrolytic stability good solubility in various solvents

28 Isostearic acid (Emersol (R) 874) H Typical composition [%] Straight Chain C Straight Chain C 12 Branched Chain C Straight Chain C 14 - Branched Chain C Straight Chain C Branched Chain C Straight Chain C Cyclic C C 20 Straight Chain 0.2 Aromatic C

29 Hydroalkylation of oleic acid with isopropyl chloroformate and Et 3 Al 2 Cl H 73% 1. Cl, Et 3 Al 2 Cl 3, CH 2 Cl 2, -15 C (1h), r.t. (1h) 2. H 2 + H H U. Biermann, J.. Metzger, Angew. Chem. 1999, 111, ; J. Am. Chem. Soc. 2004, 126,

30 Mechanism of hydroalkylation Cl Cl Al Et Cl - C 2 EtAlCl 3 R R' Cl 3 Al CH 2 CH 3 H R R' - CH 2 CH 2, AlCl 3 R R' R R' R R' R,R' = alkyl

31 New Syntheses with Unsaturated Fatty Acids Cl (CH 2 ) 6 CH CH 3 (CH 2 ) 5 (CH 2 ) 5 CH 3 CH 3 (CH 2 ) 7 (CH 2 ) 7 CH CH 3 (CH 2 ) 8 (CH 2 ) 7 CH H 3 C(CH 2 ) 8 (CH 2 ) 5 CH H 3 C(CH 2 ) 7 (CH 2 ) 7 CH (CH 2 ) 7 CH H 3 C(CH 2 ) 8 (CF 2 ) 7 CF 3 (CH 2 ) 7 CH R (CH 2 ) 7 CH 3 R CH 3 (CH 2 ) 8 (CH 2 ) 7 CH Me ( )n ( )n Me

32 Calendula officinalis CH

33 Diels-Alder Reaction CMe 78 % +, 150 C, 2h CMe

34 X-Ray Structure Analysis of the Diels-Alder Adduct

35 Tung il CH α-eleostearic acid

36 Vernonia oil from Vernonia galamensis Vernonia oil is a naturally occuring epoxidized vegetable oil. Because of this unique characteristic vernonia oil is an attractive raw material for oleochemistry. Vernonia galamensis is a shrublike plant, which originates from tropical and subtropical Africa. Nowadays it is cultivated in Zimbabwe, Kenia, Ethiopia and in parts of South America. The seeds contain 40% of oil. Hydrolysis of vernonia oil yields: 80% vernolic acid 12% linolenic acid 4% oleic acid 2% stearic acid 2% palmitic acid CH 3 (CH 2 ) 4 (CH 2 ) 7 CH (+)-vernolic acid (cis-12,13-epoxy-cis-9-octadecenoic acid)

37 Synthesis of methyl cis-12,13-epiminooleate H CH 3 (CH 2 ) 4 (CH 2 ) 7 CCH 3 CH 3 (CH 2 ) 4 (CH 2 ) 7 CCH 3 + NaN 3, NH 4 Cl EtH, H 2 + N 3 34% CH 3 (CH 2 ) 4 N H (CH 2 ) 8 CCH 3 37% + polym. PPh 3, THF 70% H N CH 3 (CH 2 ) 4 (CH 2 ) 7 CCH 3 S. Fürmeier, J.. Metzger, Eur. J. rg. Chem. 2003,

38 Agenda 21 Chapter 4 CHANGING CNSUMPTIN PATTERNS 4.18 Reducing the amount of energy and materials used per unit in the production of goods and services can contribute both to the alleviation of environmental stress and to greater economic and industrial productivity and competitiveness.

39 Gross energy requirements of important base chemicals Adipic acid Acetaldehyde Ammonia from natural gas Acetone Adipic acid Process energy Raw material Acetic acid Acetic acid Benzene Ethylbenzene Ethylene oxide Propylene oxide Rape seed oil Ethanol from corn Rape seed oil Ethylene oxide Methanol from natural gas Ethylene from naphtha n-butanol Ethanol from naphtha Propylene oxide GER / GJ t -1 M. Patel, 1999

40 Propylene xide > 4 Mill. t/a Propylene oxide Polyether polyoles (for polyurethanes) 70% Propylene glycol (for polyesters) 22% H R H H 2 N R NH 2 HC _ R _ CH

41 Epoxidation of a vegetable oil 2 / cat. HCH / H 2 2

42 Adipic Acid: 2.3 Million t/a; GER 80 GJ/t CH 2 /Catalyst + 3 Pelargonic acid CH HC CH + Azelaic acid HC(CH 2 ) n CH n = 4 (from petroselinic acid) ; n = 11 (from erucic acid)

43 Agenda 21 Chapter 4 CHANGING CNSUMPTIN PATTERNS develop criteria and methodologies for the assessment of environmental impacts and resource requirements throughout the full life cycle of products and processes. Life Cycle Analysis (LCA) Environmental Performance Metrics for Daily Use in Synthetic Chemistry (EATS), Chem. Eur. J., 2002, 8,

44 angew M. Eissen, J.. Metzger, E. Schmidt, U. Schneidewind, 10 Years after Rio Concepts on the Contribution of Chemistry to a Sustainable Development, Angew. Chem. Int. Ed. 2002, 41,

45 Acknowledgement The contributions of Dr. Ursula Biermann, Dr. Ursula Linker, Dr. Sandra Fürmeier and Dr. Ralf Mahler are gratefully acknowledged. I thank Prof. Dr. S. Lang, Braunschweig, Prof. Dr. M. Rüsch gen. Klaas, Neubrandenburg, Prof. Dr. M. S. Schneider, Wuppertal, Prof. Dr. H. J. Schäfer, Münster, Prof. Dr. S. Warwel, Münster, for cooperation. Financial support was given by the Fachagentur Nachwachsende Rohstoffe, Deutsche Bundesstiftung Umwelt and Deutsche Forschungsgemeinschaft.