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New Syntheses with Oils and Fats as Renewable Feedstocks
for the Chemical Industry
Green Chemistry: Development of Sustainable ProcessesRostock, 30. 3. – 1. 4. 2005
http://www.chemie.uni-oldenburg.de/oc/metzger
- Introduction
- Oleochemistry
- C,C-Bond forming additions
- New oil crops
- New base chemicals
- Conclusion
The twelve principles of green chemistry
7. A raw material of feedstock should be renewable
rather than depleting wherever technically and
economically practicable.
Agenda 21Chapter 4
CHANGING CONSUMPTION PATTERNS
…encouraging the environmentally sound and
sustainable use of renewable natural resources.
Feedstocks of the Chemical Industry in Germany (1991)
Renewables1,8 Mio. t
8%
Coal0,5 Mio. t
2%
Natural gas1,7 Mio. t
8%
Petroleum18,4 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 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.
Targets of Biobased Products in the USA
0%
5%
10%
15%
20%
25%
30%
2001 2010 2020 2030Jahr
Prop
ortio
n of
the
tota
l pro
duct
ion
in %
EnergyFuels
Organic chemicals
Vision for Bioenergy & Biobased Products in The United States, Biomass Research and Development Technical Advisory Comitee, October 2002, http://www.bioproducts-bioenergy.gov/pdfs/BioVision_03_Web.pdf.
Renewable Feedstocks of the Chemical Industry in Germany (2002)
Fats and Oils 900.000 t
47%
S tarch600.000 t
31%
Cellulose250.000 t
13%Others100.000 t
5%
S ugar70.000 t
4%
World Consumption of Oils and Fats (2002, mil mt)
120.3
97.4
16.86.1
Total Food Chemistry Feed81 % 14 % 5 %
World Consumption of Mineral Oil in 2002: approx. 4.000 mil mt
Raw Materials
World Production of Oils and Fats 2002 (120.3 mil mt)vegetable (approx. 80%)animal (approx. 20 % declining)
24.0
6.16.38.4
29.7
24.9
13.3
7.6 16
Soy
Palm Rape
Sunflower
Tallow
Butter
Lauric
s
Other
Laurics: Coconut and palm kernel – C12
0 1 2 32 7 12 15 15 41 101 15 15 71 60 20 94 28 614 84 54 28 53 613 46 6
double bonds C18Material 8 10 12 14 16 18 20 22coconut oil 8 7 48 17 9 10palm kernel oil 4 5 50 15 7 18palm oil 2 42 56rape oil (old) 2 38 7 51rape oil (new) 4 90 2 3sunflower (old) 6 93sunflower (new) 4 93 1soy oil 8 91lard 1 31 65 2
Carbon Chain
O
O
O
O
O
O
glycerolbackbone fatty acids
Distribution of Fatty Acids in Triglycerides
Chemical Conversion of Triglycerides: Splitting
RO
O+
OH
OH
OH
RO
O
RO
O
[cat]∆T
O
O
O
O
O
O3+ R OH
water + fatty acids
+ fatty acid methyl ester
Triglyceride + glycerol
Triglyceride + methanol glycerol
Fatty Alcohols
ROO CuO/Cr2O3
HO+ H2 + ROH200-250°C; 250 bar
- 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 Olefins: Hydroformylation/Reduction
- share of natural sources is rising
ROO
HO+ H2+ ROH
ZnO/Cr2O3
Alkyl Polyglycosides (APG)
OHO
OHOH
HOHO
OH
+
O
OHOH
HO
O
O
OHOH
OH
HOO
- nonionic surfactant- very good biodegradability- good skin compatability
detergent for home care applicationscosmetics
- 70.000 t/a
Oleochemical Production Flow Scheme
Raw Materials
oils&
fats
fattyalcohols
glycerol
Oleochemicals Specialties
fattyacids
fatty acidmethylester
sulpho fatty acid esters
triacetinpartial glycerides
conjugated fatty acidsalkyl epoxyestersdimer acidsfatty acids ethoxylatesazelaic/pelargonic acidsfatty acid esters
guerbet alcoholsalkyl chloridesfatty alcohol ethoxylatesfatty alcohol sulfatestechnical estersalkyl polyglycosides
COOH
COOH
COOH
COOH
COOHOH
COOH
9
6
13
12 9
9
10
Unsaturated fatty acids
+ CH3COOH
Mn(OAc)3/KOAc/HOAc70 - 100°C
COOMeO
O
COOMe
43%
9
+regioisomer
9
J.O. Metzger, U. Linker, Fat Sci. Technol. 1991, 93, 244-249
Manganese(III)acetate initiated radical additionof acetic acid to methyl oleate
CH2COOH
+ COOMe
I
O
O
COOMe
+ Cu- Mel
COOMe10
[(cis)] : [(trans)] = 1.3 : 1
100 - 130 °C86%
J.O. Metzger, R. Mahler, G Francke, Liebigs Ann. 1997, 2303-2313
Copper initiated addition of methyl2-iodopropanoate to methyl 10-undecenoate
No solvent!
Mechanism of the copper initiated addition of activated iodoalkanes to alkenes
R
I
R R
+ Cu- CuI
R = alkyl, (CH2)8COOMe)
I CH2CO2Me
CH2CO2Me
MeO2CI CH2CO2Me
MeO2C-MeIO
O
R
J.O. Metzger, R. Mahler, A. Schmidt, Liebigs Ann. 1996, 693-696
Synthesis of perfluoroalkyl branched octadecanoic acids
+ RFI
Cu / 130°C orPb / Cu(OAc)2, MeOH, r.t. orSnCl2 / AgOAc, MeOH, r.t.
COOMe
I
RF
109
1. H2, Pd / C2. KOH / H2O
COOHRF
109
COOMe9
RF = C4F9, C6F13, C8F17 + 10-perfluoroalkyl isomer
yield 80 - 85 %
Dimethylaluminum chloride induced addition offormaldehyde to petroselinic acid
OH
O
7 6
73%1. (CH2O)n, Me2AlCl, CH2Cl2 2 h, r.t.2. H2O
OH
O
OH
7
81
2OH
OHO
+
5
6
petroselinic acid : paraformaldehyde : Me2AlCl = 1: 2 : 2
[1] : [2] = 55 : 45
J.O. Metzger, U. Biermann, Synthesis 1992, 463-465.
OMe
O
OCl810
+
+ (CH2O)n
1. AlCl3, CH2Cl2, 24 h, r.t.2. H2O86%
1
O
OMe
OCl
+ regioisomers
10 8
2
methyl oleate : paraformaldehyde : AlCl3 = 2 : 4 : 1
COOMe
[1] :[2] = 3 : 1
J.O. Metzger, U. Biermann, Bull. Soc. Chim. Belg. 1994, 103, 393-397
AlCl3 induced addition of formaldehyde to methyl oleate
Mechanism of AlCl3 induced Prins-type reaction
+ H2C = O + AlCl3
O
OH-
H2CO
O
Cl
- AlCl2OH
AlCl3H
H
Cl3Al O = CH2
Cl Al-OCl Cl
AlCl3 induced reaction of heptanal and methyl ricinoleate
H
O
76%AlCl3, CH2Cl2RT, 4 h
+COOMeOH
9
O
H3CO
O
Cl
12
9
AlCl3 induced tetrahydropyran formation
R R´- AlCl2OH
C OR
HHO
R
HOC
HR
O AlCl2Cl
R´
R = (CH2)5CH3; R´=(CH2)7COOCH3
+ + AlCl3 O
OCH3O
Cl
912 1´1´
12
9
J.O. Metzger, U. Biermann, Liebigs Ann. 1993, 645-650
EtAlCl2 induced acylations of oleic acid
O
OH
OR O
+
1. EtAlCl2, CH2Cl2, 24 h, r.t.2. H2O
R = Me, nC6H13, nC15H31, cC3H5, Ph, ,S
10
ClR
40-58%
+ regioisomer
COOH9
HC CH
Me
Alkyl branched fatty acids
OH
O
good spreadabilitygood solubility in cosmetic formulations
good emolliencylow viscosity
low pour pointsgood oxidative and hydrolytic stability
good solubility in various solvents
Characteristics of alkyl branched fatty compounds
Isostearic acid (Emersol(R) 874)
5.6Aromatic C18
0.2C20 Straight Chain13.9Cyclic C18
2.4Straight Chain C18
68.3Branched Chain C18
5.0Straight Chain C16
4.0Branched Chain C16
0.2Straight Chain C14
-Branched Chain C14
0.3Straight Chain C12
0.1Straight Chain C10
Typical composition [%]
OH
O
Hydroalkylation of oleic acid withisopropyl chloroformate and Et3Al2Cl3
U. Biermann, J.O. Metzger, Angew. Chem. 1999, 111, 3874-3876;J. Am. Chem. Soc. 2004, 126, 10319-10330.
73%1. , Et3Al2Cl3, CH2Cl2,
-15°C (1h), r.t. (1h)
2. H2O
O Cl
O
OH
O910
OH
O
OH
O+
O Cl
OAl Et
Cl
Cl
R R' R R'
R R'
- CO2
Cl3Al CH2CH3
CH2 CH2- , AlCl3 R R'
H
R,R' = alkyl
R R'
EtAlCl3
Mechanism of hydroalkylation
New Syntheses with Unsaturated Fatty Acids
)n()n(O O
OMeMeO
R (CH2)7CH3
(CH2)7COOH
O
CH3(CH2)5 (CH2)5CH3
Cl(CH2)6COOH
O
CH3(CH2)8 (CH2)7COOH
OR
(CH2)7COOHCH3(CH2)8
CH3(CH2)7 (CH2)7COOH
O
O
(CF2)7CF3
(CH2)7COOHH3C(CH2)8
O
H3C(CH2)8 (CH2)5COOH
H3C(CH2)7 (CH2)7COOH
COOH1012 8
Calendula officinalis
Diels-Alder Reaction
COOMe
O
COOMe
O O
O OO
78 %
12 10 8
, 150°C, 2h+
X-Ray Structure Analysis of the Diels-Alder Adduct
Tung Oil
COOH9
13 11
α-Eleostearic acid
Vernonia oil from Vernonia galamensis
O
CH3(CH2)4 (CH2)7COOH
(+)-vernolic acid (cis-12,13-epoxy-cis-9-octadecenoic acid)
The seeds contain 40% of oil.Hydrolysis of vernonia oil yields: 80% vernolic acid12% linolenic acid4% oleic acid2% stearic acid2% palmitic acid
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.
Vernonia oil is a naturally occuring epoxidized vegetable oil. Because of this unique characteristic vernonia oil is an attractive raw material for oleochemistry.
Synthesis of methyl cis-12,13-epiminooleate
CH3(CH2)4
OH
N3
(CH2)7COOCH3
O
CH3(CH2)4 (CH2)7COOCH3
+ NaN3, NH4Cl EtOH, H2O
NH
(CH2)8COOCH3CH3(CH2)4
+
34%
37%
HN
CH3(CH2)4 (CH2)7COOCH3
+ polym. PPh3, THF
70%
S. Fürmeier, J. O. Metzger, Eur. J. Org. Chem. 2003, 649 – 659.
Agenda 21
Chapter 4
CHANGING CONSUMPTION PATTERNS
4.18 Reducing the amount of energy and materialsused 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.
Gross energy requirements of important base chemicals
Ethanol from corn
Ethanol from naphtha
Propylene oxiden-Butanol
Methanol from natural gas
Ethylene from naphtha
Ethylbenzene
Acetic acidBenzene
Adipic acid
Acetone
Acetaldehyde
Ammonia from natural gas
Ethylene oxide
Rape seed oil
0 20 40 60 80 100
Rape seed oil
Propyleneoxide
Ethyleneoxide
Acetic acid
Adipic acid
GER / GJ t-1
Process energyRaw material
M. Patel, 1999
Propylene Oxide
Polyether polyoles (for polyurethanes) 70%
Propylene glycol (for polyesters) 22%
HO R OH
> 4 Mill. t/a Propylene oxide
H2N R NH2
HOOC_R_COOH
Epoxidation of a vegetable oil
O
O O
O
O O O
O
O O O O
O
O
O
O
O
O
HCOOH / H2O2O2/ cat.
Adipic Acid: 2.3 Million t/a; GER 80 GJ/t
O2/Catalyst + O3
HOOC(CH2)nCOOH
n = 4 (from petroselinic acid) ; n = 11 (from erucic acid)
COOH
COOH HOOC COOH+Azelaic acidPelargonic acid
Agenda 21
Chapter 4CHANGING CONSUMPTION PATTERNS
4.20 .... 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 (EATOS), Chem. Eur. J., 2002, 8, 3580-3585.
angew
M. Eissen, J. O. 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, 414 – 436.
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 FachagenturNachwachsende Rohstoffe, Deutsche BundesstiftungUmwelt and Deutsche Forschungsgemeinschaft.