JP6861032B2 - 糖からエチレングリコールを製造する方法 - Google Patents
糖からエチレングリコールを製造する方法 Download PDFInfo
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- JP6861032B2 JP6861032B2 JP2016575912A JP2016575912A JP6861032B2 JP 6861032 B2 JP6861032 B2 JP 6861032B2 JP 2016575912 A JP2016575912 A JP 2016575912A JP 2016575912 A JP2016575912 A JP 2016575912A JP 6861032 B2 JP6861032 B2 JP 6861032B2
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- ethylene glycol
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- catalyst
- formaldehyde
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 157
- 235000000346 sugar Nutrition 0.000 title claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 70
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 69
- 239000000203 mixture Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000000197 pyrolysis Methods 0.000 claims description 43
- 239000003054 catalyst Substances 0.000 claims description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000008163 sugars Chemical class 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 8
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229940015043 glyoxal Drugs 0.000 claims description 6
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229940120731 pyruvaldehyde Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 239000000047 product Substances 0.000 description 66
- 229960001031 glucose Drugs 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000037361 pathway Effects 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 ethylene, ethylene Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSNSWKAZFASRNG-WNFIKIDCSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol;hydrate Chemical compound O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O OSNSWKAZFASRNG-WNFIKIDCSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- GTZBELRIIUXTNQ-UHFFFAOYSA-N 2-hydroxyacetaldehyde Chemical group OCC=O.OCC=O GTZBELRIIUXTNQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ATFVTAOSZBVGHC-UHFFFAOYSA-N Glycolaldehyde dimer Chemical compound OC1COC(O)CO1 ATFVTAOSZBVGHC-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/202—Ethylene glycol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/205—1,3-Propanediol; 1,2-Propanediol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
- C07C47/127—Glyoxal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/185—Saturated compounds containing keto groups bound to acyclic carbon atoms containing —CHO groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
a.糖を熱分解して、熱分解生成物組成物を得るステップ;及び
b.ステップa.の熱分解生成物組成物を触媒、水素及び溶媒の存在下に水素化して、(水素化)生成物組成物を得るステップ;
c.任意選択的に、ステップb.で得られた(水素化)生成物組成物からエチレングリコールを分離(精製)するステップ、
を含む、前記方法を提供する。
C1〜C3含酸素化合物を含む熱分解生成物組成物を、US7094932B2(特許文献6)に記載のようにして、10重量%水性グルコース(D−グルコース一水和物;Sigma Aldrich)溶液の熱分解によって得た。この熱分解生成物組成物の組成を表1に示す。
表1に記載の例1の熱分解生成物組成物(15.5g)を、5%のRuを炭素に担持してなる触媒(Sigma Aldrich、0.20g)と共にオートクレーブ中に仕込んだ。このオートクレーブを水素で三回洗浄し、次いで表2に記載の各々の圧力に水素で加圧した。この混合物を15分間の間で室温から80℃に加熱し、そして6時間攪拌した。次いで、このオートクレーブを室温に冷却して、水素圧の減少を記録した。
例2〜4に記載の方法を、基質(例1の熱分解生成物組成物)としてエチレングリコールまたはプロピレングリコールを用いて繰り返した。圧力は、30または90bar、温度は120℃または140℃、反応時間は3時間とした。結果を表3に示す。
グリコールアルデヒドダイマー(1.0g)を脱イオン水(14.5g)中に溶解した。この溶液を、5%のRuを炭素上に担持してなる触媒(Sigma Aldrich、0.20g)と共にオートクレーブ中に仕込んだ。このオートクレーブを水素で三回洗浄し、次いで表4に記載の圧力に水素で加圧した。この混合物を15分間の間で室温から80℃に加熱し、そして3時間攪拌した。次いで、このオートクレーブを室温に冷却して、水素圧の減少を記録した。
参考例9の方法を30barの圧力下に繰り返した。
参考例10の方法を100℃の温度下に繰り返した。
1.
エチレングリコールの製造方法であって、次のステップ
a.糖を熱分解して、熱分解生成物組成物を得るステップ;及び
b.触媒及び溶媒の存在下にステップa.の熱分解生成物組成物を水素化するステップ;を含み、ステップb.の反応の圧力が40bar以上である、前記方法。
2.
ステップb.の生成物が精製される、上記1に記載の方法。
3.
ステップa.の糖が、グルコース、スクロース、フルクトース、キシロース、マンノース、アラビノース及びガラクトースからなる群から選択される一種以上の糖を含む、上記1または2に記載の方法。
4.
ステップb.の溶媒が、水、アルコール、及び水とアルコールからなる群から選択される、上記1〜3のいずれか一つに記載の方法。
5.
アルコールが、メタノール、エタノール、エチレングリコール及びプロピレングリコールからなる群の一種以上から選択される、上記4に記載の方法。
6.
熱分解生成物組成物がホルムアルデヒドを含む、上記1〜5のいずれか一つに記載の方法。
7.
熱分解生成物組成物が、グリコールアルデヒド、グリオキサール、ピルブアルデヒド及びアセトールからなる群から選択される一種以上のC2〜3含酸素化合物を含む、上記1〜6のいずれか一つに記載の方法。
8.
ステップb.の触媒が、ルテニウム、ルテニウム合金、パラジウム、白金及びニッケルからなる群から選択される金属成分を含む、上記1〜7のいずれか一つに記載の方法。
9.
ステップb.の触媒金属成分が、1:1〜1:15のホルムアルデヒド:触媒金属成分の比率で存在する、上記1〜8のいずれか一つに記載の方法。
10.
ステップb.が、30bar〜120barの圧力で行われる、上記1〜9のいずれか一つに記載の方法。
11.
ステップb.が、40℃〜160℃の温度で行われる、上記1〜10のいずれか一つに記載の方法。
12.
ステップb.におけるC2含酸素化合物からエチレングリコールへの転化率が少なくとも70%である、上記1〜11のいずれか一つに記載の方法。
13.
ステップb.におけるC2含酸素化合物からエチレングリコールへの選択率が少なくとも75%である、上記1〜12のいずれか一つに記載の方法。
14.
ステップa.の熱分解生成物組成物が、1:2〜1:20のホルムアルデヒド:グリコールアルデヒドの比率でホルムアルデヒドを含む、上記1〜13のいずれか一つに記載の方法。
15.
ステップb.の生成物が、0.01:1以下の1,2−BDO:エチレングリコール重量/重量比を含む、上記1〜14のいずれか一つに記載の方法。
16.
ポリマー、ポリエチレンテレフタレート、ポリエステル樹脂、繊維またはフィルムの製造のための、上記1〜15のいずれか一つに従い製造されるエチレングリコールの使用。
17.
防氷剤、冷却剤、凍結防止剤または溶媒としての、上記1〜15のいずれか一つに従い製造されたエチレングリコールの使用。
Claims (17)
- エチレングリコールの製造方法であって、次のステップ
a.糖を熱分解して、熱分解生成物組成物を得、ここで前記熱分解生成物組成物は、ホルムアルデヒド、グリコールアルデヒド及びピルブアルデヒドを含むステップ;及び
b.触媒及び溶媒の存在下に熱分解生成物組成物を水素化するステップ;
を含み、ステップb.の反応の水素化圧が40bar以上であり、
前記触媒が、担持された触媒金属成分を含む、前記方法。 - 水素化反応の生成物が精製される、請求項1に記載の方法。
- 糖が、グルコース、スクロース、フルクトース、キシロース、マンノース、アラビノース及びガラクトースからなる群から選択される一種以上の糖を含む、請求項1または2に記載の方法。
- 溶媒が、水、アルコール、及び水とアルコールからなる群から選択される、請求項1〜3のいずれか一つに記載の方法。
- アルコールが、メタノール、エタノール、エチレングリコール及びプロピレングリコールからなる群の一種以上から選択される、請求項4に記載の方法。
- 熱分解生成物組成物が、グリオキサール、アセトール及び酢酸からなる群から選択される一種以上のC2〜3含酸素化合物を更に含む、請求項1〜5のいずれか一つに記載の方法。
- 触媒が、ルテニウム、ルテニウム合金、パラジウム、白金及びニッケルからなる群から選択される金属成分を含む、請求項1〜6のいずれか一つに記載の方法。
- 触媒が、炭素担体に担持されたルテニウム触媒を含む、請求項1〜7のいずれか一つに記載の方法。
- 触媒金属成分が、1:1〜1:15のホルムアルデヒド:触媒金属成分の比率で存在する、請求項1〜8のいずれか一つに記載の方法。
- 水素化が、40bar〜120barの圧力で行われる、請求項1〜9のいずれか一つに記載の方法。
- 水素化が、40℃〜160℃の温度で行われる、請求項1〜10のいずれか一つに記載の方法。
- 水素化におけるC2含酸素化合物からエチレングリコールへの転化率が少なくとも70%である、請求項1〜11のいずれか一つに記載の方法。
- ステップb.におけるC2含酸素化合物からエチレングリコールへの選択率が少なくとも75%である、請求項1〜12のいずれか一つに記載の方法。
- ステップa.の熱分解生成物組成物が、1:2〜1:20のホルムアルデヒド:グリコールアルデヒドの比率でホルムアルデヒドを含む、請求項1〜13のいずれか一つに記載の方法。
- 水素化の生成物が、0.01:1以下の1,2−ブタンジオール:エチレングリコール重量/重量比を含む、請求項1〜14のいずれか一つに記載の方法。
- 2ステッププロセスであり、そしてステップa.の熱分解生成物組成物がステップb.で直接水素化される、請求項1〜15のいずれか一つに記載の方法。
- 熱分解生成物組成物中のC2含酸素化合物の割合が10重量%以上である、請求項1〜16のいずれか一つに記載の方法。
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