The Use of Renewable Feedstock in Organic Synthesis
Transcript of The Use of Renewable Feedstock in Organic Synthesis
1
The Use of Renewable The Use of Renewable The Use of Renewable The Use of Renewable
Feedstock in Organic Feedstock in Organic Feedstock in Organic Feedstock in Organic
Synthesis Synthesis Synthesis Synthesis
Dr. Dr. Dr. Dr. LajosLajosLajosLajos KovKovKovKováááácscscscs
DepartmentDepartmentDepartmentDepartment ofofofof MedicinalMedicinalMedicinalMedicinal ChemistryChemistryChemistryChemistry
UniversityUniversityUniversityUniversity ofofofof Szeged, HungarySzeged, HungarySzeged, HungarySzeged, Hungary
Chemical Biology Chemical Biology Chemical Biology Chemical Biology CCCCourseourseourseourse, , , , SeiliSeiliSeiliSeili, , , , FinlandFinlandFinlandFinland
Tuesday, 26 AugustTuesday, 26 AugustTuesday, 26 AugustTuesday, 26 August, 2008, 2008, 2008, 2008
Chem. Eng. News, 86(23), August 18,
2008: thematic issue on Sustainability.
2
What is sustainable development?
“… sustainable development is development that meets t he needs of the present without compromising the ability of future generations to meet their own needs.”
Brundtland Commission (1987): Our common future
F.W. Lichtenthaler,S. Peters,C. R. Chimie, 2004, 7, 65-90.
Raw materials basis of chemical industry in a historical perspective
3
The amount and nature of annually produced biomass
World’s biomass production (t/a): 170−200×109
Sugar:0.17×109
Wood: 13×109
Lignocellulose: 50×109
Harvested wood:1.55×109
Cellulose:0.15×109
Cereals: 1.8×109
Starch:1.1×109
D-Glucose:5×106
Paradigm shift and the ensuing conflicts
BiomassFossilmaterials
Energy
Food
Chemicals
• increasing use of biomass instead of fossil materials• potential competition between food, energy crops for
land use and carbon-based consumer products (chemicals)
4
G. A. Olah,A. Goeppert,G. K. S. Prakash: Beyond Oil and Gas: The Methanol Economy, Wiley-VCH, Weinheim, 2006
The World’s primary energy consumption, 1970 to 2025
“The generation, storage, and transport of energy are among the greatest challenges, if not the most formidable challenge at all, for years to come.”
A. Taubert, Guest Editor, in his Editorial for the special issue of International Journal of Molecular Sciences devoted to "Energy Technology for the 21st Century - Materials and Devices“, 2008, http://www.mdpi.org/ijms/specialissues/energytec.htm
Oláh’s proposed solution: the methanol economy®
G. A. Olah, A. Goeppert, G. K. S. Prakash: Beyond Oil and Gas: The Methanol Economy, Wiley-VCH, Weinheim, 2006
5
Challenges for a sustainable development
Production of carbon based consumer products from renew able resources
Carbon dioxide (CO 2)
Biomass
Molecular level understanding of pollution preventi on
Green chemistry
Using Nature forCO2 conversion
Cheap H2
Replacement of fossil fuels for energy
Hydrogen economy (generation, storage, and transportat ion of H 2),solar power
Sustainable liquid (methanol, ethanol, etc.) economy
Sustainable and green chemistry
Chemistry
Sustainable chemistry
Green chemistry
Sustainable andgreen chemistry
6
The principles of sustainable/green chemistryGreen chemistry is the utilization of a set of principles that reduces or
eliminates the use or generation of hazardous substances in the design, manufacture, and applications of chemical products.
1. It is better to prevent waste than to treat or c lean up waste after it isformed.
2. Synthetic methods should be designed to maximize the incorporationof all materials used in the process into the final product.
3. Wherever practicable, synthetic methodologies sh ould be designed touse and generate substances that process little or no toxicity tohuman health and the environment.
4. Chemical products should be designed to preserve efficacy offunction while reducing toxicity.
5. The use of auxiliary substances ( e.g. solvents, separation agents, etc.)should be made unnecessary wherever possible and, i nnocuous whenused.
6. Energy requirements should be recognized for thei r environmentaland economic impacts and should be minimized. Synt hetic methodsshould be conducted at ambient temperature and pres sure.
Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice, Oxford University Press, Oxford, 1998
(continued)
7. A raw material of feedstock should be renewable r ather than depletingwherever technically and economically practicable.
8. Unnecessary derivatization (blocking group, prot ection/deprotection,temporary modification of physical/chemical process es) should beavoided whenever possible.
9. Catalysts (as selective as possible) are superio r to reagents.10. Chemical products should be designed so that at the end of their function
they do not persist in the environment and break do wn into innocuousdegradation products.
11. Analytical methodologies need to be further dev eloped to allow for real-time, in-process monitoring and control prior to th e formation ofhazardous substances.
12. Substances and the form of a substance used in a chemical processshould be chosen so as to minimize the potential fo r chemical accidents,including releases, explosion, and fires.
Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice, Oxford University Press, Oxford, 1998
The principles of sustainable/green chemistry
7
Fossil vs. renewable materials
• Fossil (depleting) materials (petroleum oil, natural gas, tar-sand, shale bitumen, coals) are mixtures of hydrocarbons. When oxidized (combusted) they form carbon dioxide (CO2) and water (H2O) and thus are not renewable on the human scale.
• Renewable feedstocks (biomass), in contrast, will re-grow annually. They are much more varied in their composition (carbohydrates, vegetable oils and animal fats, terpenes, lignins etc.). As a rule, they are usually more oxygenated than their fossil counterparts.
Biomass use in more detail
“The term “biomass” means any organic matter that is available on a renewable or recurring basis (excluding old-growth timber),including dedicated energy crops and trees, agricultural food and feed crop residues, aquatic plants, wood and wood residues, animal wastes,and other waste materials.”
B. Kamm, P. R. Gruber, M. Kamm(2005): Biorefineries – Industrial Processes and Products, in Ullmann’sEncyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, Vol. 4, p. 101-133.
8
Model of a product flow-chart for biomass feedstock
E. M. Rubin (2008): Genomics of cellulosic biofuels. Nature 454, 841-845 doi:10.1038/nature07190
Biology of bioconversion of solar energy into biofuels
9
Structure of lignocellulose
E. M. Rubin (2008): Genomics of cellulosic biofuels.
Nature 454, 841-845 doi:10.1038/nature07190
OO O
OO
OOO OH
H
OO
OH
O O
O
H
H
H
H
H
H
Products of a lignocellulosic feedstock biorefinery
10
The major biomass components as a renewable feedstock for the chemical industry
A. Corma, S. Iborra, A. Velty (2007): Chemical routes for the transformation of biomass into chemicals. Chem. Rev., 107, 2411-2502.
• Carbohydrates (cellulose, hemicellulose etc.) 75 %
• Lignin 20 %
• Proteins, nucleic acids, fats and oils, terpenes,alkaloids etc. 5 %
• Only 3 to 3.5 % (ca. 6×109 t) of this amount is used in non-food applications, e.g. chemistry
Biotechnological sugar-based product family tree
11
The use of carbohydrates: pros and cons
• inexpensive materials• available from virtually
inexhaustible, renewable sources
• they are rich in chiralcenters
• too many hydroxyl groups– most often protecting
groups are required
• too many chiral centers• too few reactive
functional groups (C=C, C=O)
• the price of more complex carbohydrates has not been competitive with petrochemicals for a long time
Carbohydrates: major transformation pathways
• Chemicals from Fermentation Processes: Glucose Fermentation– Lactic Acid Platform– Succinic Acid Platform– 3-Hydroxypropionic Acid Platform– Itaconic Acid Platform– Glutamic Acid Platform
• Chemical Transformations of Monosaccharides– Dehydration of Monosaccharides
• Chemical Transformation of Disaccharide (Sucrose etc.)– Hydrolysis– Esterification– Etherification– Oxidation– Glucosyl Shift: Production of Isomaltulose and Isomalt– Polymers
• Polysaccharides– Depolymerisation– Deacetylation of Chitin
12
Glucose fermentation and oxidation∆G (kcal/mol)
C6H12O6 + 2 Pi + 2 ADP → 2 CH3CH(OH)COOH + 2 H2O + 2 ATP –47C6H12O6 + 2 Pi + 2 ADP → 2 CH3CH2OH + 2 CO2 + 2 H2O + 2 ATP –47C6H12O6 + 6 O2 + 36 Pi + 36 ADP → 6 CO2 + 42 H2O + 36 ATP –680
other fermentationprocesses
Principal applications of lactic acid
Lactobacillus,Bacillus,
and Rhizopusbacteria
differentcarbohydrates
HO
CH3
O
OH
lactic acid
HO
CH3
O
O
CH3
O
OOH
CH3
O
HO
CH3
O
O
poly(lactic acid)
ethyl lactate(Vertec TM)
CH3
poly-
condensation
-H 2O
EtOH/H +
-H2 O
n
biodegradablepolymer
> 140 000 t/a
environmentally benign solvent, replacement of DMF, N-methyl-
pyrrolidone, acetone, toluene
other uses of lactic acid
13
The furan platform: furfural
O
O
pentosanes,D-xylose etc.
furfural
O
O OOH
furfurylalcohol
OOH
tetrahydro-furfurylalcohol
ONH2O
OH
OO
R
O
H
furfurylaminefuran-2-carboxylic acid
(pyromucic acid)
R = OH, furfurylideneacetic acid
R = alkyl, furfurylideneketones
furan
tetrahydrofuran
KOH(Cannizzaroreaction)
H 2/C
u
H2/Ni
H2/Ni
1. NH3
2. H2 /Ni
Pd (-CO)
CH 3COR
KOH
H2/Ni
The furan platform: 5-hydroxymethylfurfural 1.
O
OHO
hexoses(D-fructose, D-glucose),
inulin, cellulose etc.
5-hydroxymethylfurfural(HMF)
215 °C, 31 bar2-5% H2SO4,15 sec
H3C O CH3
OOHHO
OOHHO
ONH2H2N
OOO
2,5-dimethylfuran
O
OOHHO
OO
furan--2,5-dicarboxaldehyde
4-oxopentanoic acid(levulinic acid)
2,5-bis(hydroxymethyl)furanfuran-2,5-dicarboxylic acid
5-hydroxymethylfuran--2-carboxylic acid
2,5-bis(aminomethyl)-furan
O
H3CO
OH
OH
H3CO
OH H3C OO
4-hydroxypentanoic acid(4-hydroxyvaleric acid)
γ-valerolactone(GVL)
Ag2O
100 °C
1. NH2OH2. H2/Ni
H2/Pt
O2 /Pb-Pt
H2 , Cu-Ru/C193 °C
, 14,6 bar
12 min
H2, Ru(acac)3, Bu3PNH4PF6
2-5%
H 2SO 4
BaMnO 4
60-70%
H
-H2O H3C CH3
O Oacac =
14
γ-Valerolactone (GVL) from biomass
I. T. Horváth, H. Mehdi, V. Fábos, L. Boda, L. T. Mika (2008): γ-Valerolactone -a sustainable liquid for energy and carbon-based chemicals. Green Chem., 10, 238-242.
Research octane number
(RON): 130
M. Mascal, E. B. Nikitin, Angew. Chem. Internatl. Ed. Engl. (2008): Direct, high-yield conversion of cellulose into biofuel, 47, published online: Aug 1 2008 4:00AM, DOI: 10.1002/anie.200801594.
The furan platform: 5-hydroxymethylfurfural 2.
energy density (kWhL-1)5-ethoxymethylfurfural (EMF): 8.7
ethanol: 6.1gasoline: 8.8
diesel fuel: 9.7
15
Dehydration of monosaccharides to furans and levulinic acid
Glucosyl shift: production of artificial sweeteners isomaltulose and Isomalt
HO
OH
OH
O
OH
O
OHHO
HO
HOO
O
OHHO
HO
HOO
OH
OH
OHHO
OH
isomalt
OH
OHHO
OO OH
OHHO
HO
HOO
isomaltulose
sucrose
Protamino-bacterrubrum
2
6
1
1
6 2
Ni/H2
1
2
6
Palatinit®,C*Isomaltidex®
60 000 t/a
16
Glycosidase inhibitors used as drugs
NH
OH
HO
HO
HO
OH
OH
OCOOH
HO
HO
HN
AcHN
OHH
NHH2N
Zanamivir (Relenza®)
COOEt
O
H2N
AcHN
oseltamivir (Tamiflu®)
NR
OH
HO
HO
acarbose(Glucobay®/Precose®/Prandase®)
voglibose(Basen®/AO-128/Volix)
R = CH2CH2OHmiglitol (Glyset®/Diastabol®)
R= n-BuN-butyldeoxynojirimicin(miglustat/Zavesca®)
HO OH
O
HO OH
OHO
HOO
HO
O
HO OH
NH
HO OH
OH3CHO
HO
HO
HO
Other industrial carbohydrate-based products
O
OHHO
HOO
alkyl polyglucosides (APG)x = 0.3-0.7; n = 1-5
OHHO
HO
OO
H
O
xn
surfactants50,000 t/a
OR1
OR2
OR3
O
O
OR5R6O
R7O
R8OO
R4O
Olestra (Olean®)R1...R8 = fatty acyl 6-8/H2-0
fat replacer (‘fatless’ fat)dioxin sequestrant
17
D-Glucose derivatives as versatile building blocks
F. W. Lichtenthaler, S. Peters (2004): Carbohydrates as green raw materials for the chemical industry. C. R. Chimie 7, 65-90.
Vegetable oils, waxes and animal fats
• Reaction of the Carboxy Group– Fatty Acids– Fatty Amines– Fatty Alcohols– Glycerol
• Reaction of the Fatty Chain– Epoxidation– Ring-Opening of Epoxidized Fatty
Acid Derivatives– Hydroformylation– Dimerization– Oxidative Cleavage and
Ozonolysis– Metathesis Reactions
Picture © Craig Blacklock
18
Oleic acid to value added chemicals from metathesis reactions
Terpenes• Pinene
– Isomerization: α-Pinene– Epoxidation of α-Pinene– Isomerization of α-Pinene Oxide– Hydration of α-Pinene: α-Terpineol– Dehydroisomerization
• Limonene– Isomerization– Epoxidation: Limonene Oxide– Isomerization of Limonene Oxide– Dehydroisomerization of Limonene and
Terpenes To Produce Cymene• Carene
– Isomerization of Carene– Epoxidation of Carene– Isomerization of 2- and 3-Carene Oxides– Dehydroisomerization
• Camphene– Epoxidation of Camphene
• Citral– Aldol Condensations of Citral and Ketones– Baeyer-Villiger Oxidation: Melonal– Hydrogenation of Citral
Picture © Wikipedia
19
Some valuablecompounds that can be obtainedfrom αααα- and ββββ-
pinene
Vitamin A acetate:> 3,000 t/a
Lignins
• Production of dimethylsulfoxidefrom lignins
• Synthesis of vanillin
Picture © Craig Blacklock
20
The structure of lignins
• Main components (monomers) • Partial structure of a lignin polymer
OH
OCH3
CarbohydrateO
OCH3
CH2OH
O
CH
HCOH
CHOCHOH2C
O
CH3O
OCH3
HOH2C
O
HC
HC
OCH3
O
CH3O
HCCH
O
CHO
OH
CH2OH
O
CH
HC
HCCH
O
H2COH
CH3O
HCOHHC
O
CH2OH
OCH3
HOCH2
O
HCHC
OCH3
C
HC
OH [O-C]
CH2OH
OH
CH
HCOH
CH3O H2COH
CH3O
HC
HC
O
H2C
CH2
OH
CH
CH
O
O
CH2OH
O
CH
HCOH
OCH3
HO
OCH3
HCOH
HC
O
H2COH
CH3O
CH2OH
OH
HCCH
CH3O
O LigninCH3OO
CH2OHCH
HC
OH
OH
p-coumaryl alcohol
OOH
OH
coniferyl alcohol
OOH
O
OH
sinapyl alcohol
Vanilin from lignin
OH
OCH3
CHSO3-
OH
OCH3
CHO
[O]
alkaline oxidation
• As of 2001, the annual demand for vanillin was 12,000 tons, but only 1,800 tons of natural vanillin were produced
• Except for the early times, synthetic vanilin is produced frompetrochemical sources (eugenol or guaiacol)
• Vanilin is also produced from waste sulfite liquors from the celluloseindustry by alkaline oxidation
• In the traditional process, >160 tons of caustic waste are produced for every ton of vanillin manufactured
21
DMSO from lignine
Lignosulfonates act as methylating agents
OH
OCH3
CHSO3-
HS-
OH
OH
CHSO3-
+ CH3S-OH
OCH3
CHSO3-
(CH3)2S (CH3)2SONO2
Selected readings 1. Books
• R. J. Simmonds (1992): Chemistry of biomolecules: an introduction. Royal Society of Chemistry, Cambridge.
• B. G. Davis, A. J. Fairbanks (2002): Carbohydrate chemistry. (Series Ed: S. G. Davies. Oxford Chemistry Primers, 99.) Oxford University Press, Oxford.
• J. F. Robyt (1998): Essentials of carbohydrate chemistry. (Series Ed: C. R. Cantor. Springer advanced texts in chemistry.) Springer Verlag, New York.
• P. M. Collins, R. J. Ferrier (1996): Monosaccharides. Their chemistry and their roles in natural products.John Wiley and Sons, New York.
• S. Hanessian (Ed.) (1997): Preparative carbohydrate chemistry. Marcel Dekker, New York. • M. Bols (1996): Carbohydrate building blocks. John Wiley and Sons, New York.• J. N. BeMiller, R. L. Whistler, Eds. (1992): Industrial gums: polysaccharides and their derivatives.
Academic Press.• G. A. Olah, A. Goeppert, G. K. S. Prakash (2006): Beyond oil and gas: the methanol economy, Wiley-
VCH, Weinheim.• F. Gunstone (2004): The chemistry of oils and fats: sources, composition, properties and uses. Wiley-
Interscience, New York.• F. Shahidi Ed. (2005): Bailey's industrial oil and fat products. Volumes 1-6, 6th Edition, Wiley-
Interscience, New York.• M. Pagliaro, M. Rossi (2008): Future of glycerol. New usages for a versatile raw material. Royal Society
of Chemistry, Cambridge.• T.-L. Ho (1992): Enantioselective synthesis: natural products from chiral terpenes. Wiley-Interscience,
New York.• E. Breitmaier (2006): Terpenes: flavors, fragrances, pharmaca, pheromones. Wiley-VCH, Weinheim.• P. T. Anastas, R. H. Crabtree Eds. (2008): Handbook of green chemistry - green catalysis. Wiley-
Interscience, New York.• R. A. Sheldon, I. Arends, U. Hanefeld Eds. (2007): Green chemistry and catalysis. Wiley-Interscience,
New York.• P. Tundo, A. Perosa, F. Zecchini Eds. (2007): Methods and reagents for green chemistry: an
introduction. Wiley-Interscience, New York.
22
Selected readings 2. Reviews, papers and websites• A. Corma, S. Iborra, A. Velty (2007): Chemical routes for the transformation of biomass into chemicals. Chem. Rev.,
107, 2411-2502. See other papers in the same issue as well.• J. Szejtli (2004): Past, present, and future of cyclodextrin research. Pure Appl. Chem. 76, 1825-1845.• F. W. Lichtenthaler, S. Mondel (1997): Perspectives in the use of low molecular weight carbohydrates as organic raw
materials. Pure Appl. Chem. 69, 1853-1866.• F. W. Lichtenthaler (2002): Unsaturated O- and N-heterocycles from carbohydrate feedstocks. Acc. Chem. Res., 35,
728-737.• F. W. Lichtenthaler, S. Peters (2004): Carbohydrates as green raw materials for the chemical industry. C. R. Chimie
7, 65-90.• F. W. Lichtenthaler (2005): Carbohydrates in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim,
Vol. 5, p. 79-122.• I. T. Horváth, H. Mehdi, V. Fábos, L. Boda, L. T. Mika (2008): γ-Valerolactone - a sustainable liquid for energy and
carbon-based chemicals. Green Chem., 10, 238-242.• H. Mehdi, V. Fábos, R., A. Bodor, L. T. Mika, I. T. Horváth (2008): Integration of homogeneous and heterogeneous
catalytic processes for a multi-step conversion of biomass: from sucrose to levulinic acid, γ-valerolactone, 1,4-pentanediol, 2-methyl-tetrahydrofuran, and alkanes. Top. Catal., in press.
• Y. Román-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic (2007): Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature, 447, 982-986.
• H. Zhao, J. E. Holladay, H. Brown, Z. C. Zhang (2007): Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science, 316, 1597-1600.
• M. Mascal, E. B. Nikitin, Angew. Chem. Internatl. Ed. Engl. (2008): Direct, high-yield conversion of cellulose into biofuel, 47, published online: Aug 1 2008 4:00AM, DOI: 10.1002/anie.200801594.
• E. M. Rubin (2008): Genomics of cellulosic biofuels. Nature 454, 841-845 doi:10.1038/nature07190.• B. Kamm, P. R. Gruber, M. Kamm (2005): Biorefineries – Industrial Processes and Products, in Ullmann’s
Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, Vol. 4, p. 101-133.• Innovating for a better future. Putting sustainable chemistry into action. Implementation action plan 2006.
http://www.suschem.org/• Biotechnology Industry Organization (2006): Achieving sustainable production of agricultural biomass for biorefinery
feedstock. http://www.bio.org/• Chem. Eng. News, 86 (23), August 18, 2008: thematic issue on Sustainability.
Availability of this lecture
• http://www.mdche.u-szeged.hu/~kovacs/renewables_Seili.pdf