Epoxidation of Olefins Using Molecular...
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Epoxidation of Olefins Using Molecular
Oxygen
Zhongxing Huang
Sep 16th, 2015
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Major Challenge in Catalysis
May 31st, 1993, C&EN News.
Key points
Low temperature
Selective
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Most Ancient Chemistry-Oxygenase
Monooxygenase catalyzes the incorporation of one atom of oxygen into the product
Iron-Containing Enzymes, RSC Publishing, 2011.3
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Most Ancient Chemistry-Oxygenase
Dioxygenase incorporates both oxygen atoms into the product
Shen, B.; Gould, S. J. Biochemistry 1991, 30, 8936.
Gould, S. J.; Kirchmeier, M. J.; LaFever, R. E. J. Am. Chem. Soc. 1996, 118, 7663. 4
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Most Ancient Chemistry-Oxygenase
Dioxygenase incorporates both oxygen atoms into the product
Monooxygenase catalyzes the incorporation of one atom of oxygen into the product
Ideal system should avoid use of reductants
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Most Ancient Chemistry-Oxygenase
Dioxygenase incorporates both oxygen atoms into the product
Ideal Dioxygenase incorporates both oxygen atoms into the epoxide
Monooxygenase catalyzes the incorporation of one atom of oxygen into the product
Ideal system should avoid use of reductants
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Most Ancient Chemistry-Oxygenase
Dioxygenase incorporates both oxygen atoms into the product
Ideal Dioxygenase incorporates both oxygen atoms into the epoxide
Monooxygenase catalyzes the incorporation of one atom of oxygen into the product
Ideal system should avoid use of reductants
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Industrial Process- EO and PO
1 sulfuric acid 35954
2 nitrogen 30543
3 ethylene 25682
4 oxygen 25568
5 propylene 15345
6 chlorine 12166
7 ethylene dichloride 12163
8 phosphoric acid 11463
9 ammonia 10762
10 sodium hydroxide 9508
11 benzene 7675
12 nitric acid 6703
13 ammonium nitrate 6021
14 ethylbenzene 5779
15 urea 5755
16 styrene 5394
17 hydrochloric acid 5012
18 ethylene oxide 3772
19 cumene 3736
20 ammonium sulfate 2643
Top chemicals produced in US (2004,103 ton)
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Industrial Process- EO and PO
1 sulfuric acid 35954
2 nitrogen 30543
3 ethylene 25682
4 oxygen 25568
5 propylene 15345
6 chlorine 12166
7 ethylene dichloride 12163
8 phosphoric acid 11463
9 ammonia 10762
10 sodium hydroxide 9508
11 benzene 7675
12 nitric acid 6703
13 ammonium nitrate 6021
14 ethylbenzene 5779
15 urea 5755
16 styrene 5394
17 hydrochloric acid 5012
18 ethylene oxide 3772
19 cumene 3736
20 ammonium sulfate 2643
Top chemicals produced in US (2004,103 ton)
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Industrial Process- EO and PO
1 sulfuric acid 35954
2 nitrogen 30543
3 ethylene 25682
4 oxygen 25568
5 propylene 15345
6 chlorine 12166
7 ethylene dichloride 12163
8 phosphoric acid 11463
9 ammonia 10762
10 sodium hydroxide 9508
11 benzene 7675
12 nitric acid 6703
13 ammonium nitrate 6021
14 ethylbenzene 5779
15 urea 5755
16 styrene 5394
17 hydrochloric acid 5012
18 ethylene oxide 3772
19 cumene 3736
20 ammonium sulfate 2643
Top chemicals produced in US (2004,103 ton)
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Industrial Process- EO and PO
Ethylene Oxide (EO)
Worldwide consumption 14.7 million tons (2002)
Takes up >=10% ethylene production
US$ 1.66-1.88/kg (2006)
Washing/dyeing, electronics, pharmaceuticals, pesticides, textiles,
papermaking, automobiles, oil recovery and oil refining.
Propylene Oxide (PO)
Worldwide consumption 6.74 million tons (2003)
Takes up >=10% propylene production
US$ 1.88-2.03/kg (2006)
Polyurethane polyols (60-65%), propylene glycols (20-25%), P-series
glycol ethers (3-5%) and other
Kirk Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, 2001.11
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EO production
Chlorohydrin Process
Discovered in 1859
Phased out in 1940s
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EO production
Chlorohydrin Process
Discovered in 1859
Phased out in 1940s
Direct Oxidation methods (Ag/O2)
Patented in 1931 by Lefort
Union Carbide (first to use)
Scientific Design Co. (25% world production)
Shell (40% world production)
US Patent 6717001 B2, Apr. 2004 13
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EO production
Chlorohydrin Process
Discovered in 1859
Phased out in 1940s
Direct Oxidation methods (Ag/O2)
Patented in 1931 by Lefort
Union Carbide (first to use)
Scientific Design Co. (25% world production)
Shell (40% world production)
If you could increase the selectivity by 1% for the Shell Process, considering EO world
production as 14.7 million tons, Shell’s share as 40% and EO price as 1.66 US$/kg, the
extra earning each year would be 110 million US$.
That’s your salary working as a TA at UT for 4583 years.
US Patent 6717001 B2, Apr. 2004 14
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EO production
Origins of High temperature and selectivity
Major byproducts
(combustion)
High temp. for
active [O]
Always the paradox:
reactivity and selectivity
Ind. Eng. Chem. Res, 2006, 45, 3447. 15
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PO production
How about Ag/O2 system for PO production
Ind. Eng. Chem. Res, 2006, 45, 3447. 16
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PO production
Ind. Eng. Chem. Res, 2006, 45, 3447.
Origins of low selectivity
Lower barrier than ethene
Significant lower barrier than ethene
Another combustion pathway
Solution?
Lower temperature?
Different [O]
Different route
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PO production
Organic peroxide-mediated approaches
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PO production
Shell’s SMPO Process
SMPO Process:
1 ton PO = 2.5 ton SM
IBPO Process:
1 ton PO = 2.1 ton IB
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PO production
Sumitomo PO-only Process
Easier auto-oxidation in (1)
Faster epoxidation in (2), 7 fold as SMPO process
Exothermic epoxidation and hydrogenation, heat recovery
Key of economy: cumene loss
Sumitomo Kagaku, 2006, I. 20
2000 Bench test
2001 Pilot testing
2002 Plant completion
2003 Plant startup
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Comparison between Nature and Industry
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Comparison between Nature and Industry
EB and hydrogen as artificial NAD(P)H
Ag/oxygen system closer to ideal, but needs high temp, lacks selectivity and scope
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Untraceable chemistry
Pr(OAc)8 catalyzed aerobic epoxidation of olefinic compounds (e.g.
terpenes) in the coexistence of aldehydes (1984)
Fe(III) catalyzed aerobic epoxidation of propylene with aldehdyes
JP Patent 59-231077, 1984
Kogyo Kagaku Zasshi, 1970, 73, 99. 23
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Early discovery
Peroxy acid proposed as intermediate
Peracid decarboxylation by P450 is known
J. Chem. Soc., Chem. Commun., 1990, 1323. 24
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Systematic study of scope
Bull. Chem. Soc. Jpn., 1991, 64, 2513. 25
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Versatile system
Chem. Lett., 1992, 2109.
Suitable system for a wide range of metals
Metal complex does play a role
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Vanadium: complementary scope
Chem. Lett., 1991, 941.
Coordination of amide might be the key
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Enantioselective epoxidation
Chem. Lett., 1992, 2231. 28
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Mechanistic consideration
Chem. Lett., 1992, 2231. 29
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Study of model reaction
Chem. Lett., 1992, 2231.
Metal-oxo not likely
Involving radical pathway
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Stilbene experiments
Chem. Lett., 1992, 2231.
Metal-oxo not likely
Solely peracid not likely
Acylperoxy radical more plausible
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Stilbene experiments
Chem. Lett., 1992, 2231.
Might have two pathways
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Homogeneous Catalysis Using TM
Aldehydes as coreductants
Proposed pathways
Inorg. Chem., 1996, 35, 1045. 33
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Homogeneous Catalysis Using TM
Other coreductants
Chem. Lett., 1990, 1661.
Chem. Lett., 1990, 1657.
Chem. Lett., 1992, 2077.
Harsher condistions
Alfa-hydroxy ketones observed
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Homogeneous Catalysis Using TM
Interesting Pd/azibenzil system
JACS, 1976, 98, 6728.
Details not available
Likely stoichiometric in TMT
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Homogeneous Catalysis Using TM
Interesting Pd/azibenzil system
JACS, 1980, 102, 2129. 36
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Homogeneous Catalysis Using TM
A homogeneous analogue to SMPO process
Ishii, Chem. Commun. 2000, 163
Recap on SMPO
Auto-oxidation of EB: high T, high
pressure
Generation of organic peroxide
Ti-catalyzed epoxidation
This version
Mo-catalyzed epoxidation
Co(II) can be easily oxidized by O2 to Co(III)
Auto-oxidation assisted by NHPI
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Comparison again
Still mimic of P450 process
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Homogeneous Catalysis Using TM
Without reductant
Not fully understood
Limited studies
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Homogeneous Catalysis Using TM
Groves’ Ruthenium Porphyrin System
Manometric: 2 mol epoxide formed = 1 mol oxygen
Ru(II)(TMP)(THF)2 can catalyze the reaction
UV spectrum: little Ru(VI) and no Ru(II)
JACS, 1985, 107, 5790 40
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Homogeneous Catalysis Using TM
Groves’ Ruthenium Porphyrin System
JACS, 1985, 107, 5790 41
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Homogeneous Catalysis Using TM
Enantioselective epoxidation using Ru(VI)
CC, 1998, 1583 42
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Homogeneous Catalysis Using TM
Niobium Porphyrin system
JACS, 1985, 107, 6416 43
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Homogeneous Catalysis Using TM
Niobium Porphyrin system
JACS, 1985, 107, 6416 44
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Homogeneous Catalysis Using TM
V(IV)/V(V) system
J. Mol. Catal. A, Chem. 2002, 179, 41
Studies of ligand synthesis
Smaller reduction potential of V(IV)/V(V), higher conversion
Highest epoxidation selectivity 56%
Cyclohexene as the only case, auto-oxidation not excluded
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Homogeneous Catalysis Using TM
Dioxomolybdenum system
J. Mol. Catal. A, Chem. 2000, 156, 205
J. Mol. Catal. A, Chem. 1997, 117, 455
RSC Advance. 2012, 2, 8071 46
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Comparison again
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Comparison again
For Homogeneous catalysis
High-valent di-oxometal complexes are promising
Scope, compatibility and limitation needs to be studied
For Hetergeneous catalysis
Issues of temperatures and selectivity still need to be addressed
When will Ag/O2 process be phased out?
New form of catalysis?
Next generation method should be mild, energy-saving and universal
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