WO2020258131A1 - Method for preparing glycolic acid - Google Patents
Method for preparing glycolic acid Download PDFInfo
- Publication number
- WO2020258131A1 WO2020258131A1 PCT/CN2019/093182 CN2019093182W WO2020258131A1 WO 2020258131 A1 WO2020258131 A1 WO 2020258131A1 CN 2019093182 W CN2019093182 W CN 2019093182W WO 2020258131 A1 WO2020258131 A1 WO 2020258131A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- glycolaldehyde
- noble metal
- glycolic acid
- supported catalyst
- Prior art date
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 35
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 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 description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 2
- 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 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
Definitions
- the present invention relates to a method for preparing glycolic acid comprising oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- Glycolic acid has conventionally been used mainly as boiler compounds, cleaning agents, leather tanning agents, chelating agents of metal ions and the like. In recent years, its applications have expanded to cosmetics, personal care and pharmaceuticals for external use. Glycolic acid to be used for pharmaceuticals requires high purity grade and is desired to contain a lower level of harmful impurities. Glycolic acid has recently been expected also as a raw material for polyglycolic acid having biodegradability and a gas barrier function.
- Typical examples of a conventionally known method for producing glycolic acid include (1) a method of reacting carbon monoxide, formaldehyde and water in the presence of a strongly acidic catalyst under high-temperature and high-pressure conditions, (2) a method of reacting formaldehyde with hydrogen cyanide, (3) a method of reacting chloroacetic acid with sodium hydroxide, (4) a method of carrying out a Cannizzaro reaction between glyoxal available by oxidation of ethylene glycol and a strong alkali to form a glycolate salt, and then adding an acid to liberate glycolic acid from the resulting glycolate salt; (5) a method of carrying out a liquid-phase reaction between glyoxal available by oxidation of ethylene glycol and water in the presence of an inorganic catalyst; (6) a method for catalytic oxidation of ethylene glycol in the presence of a noble metal catalyst and oxygen; and (7) a method of carrying out oxidative esterification of ethylene glycol with methanol
- the method (1) is performed in the presence of a strongly acidic catalyst such as acidic polyoxometalate under high-temperature and high-pressure conditions.
- a strongly acidic catalyst such as acidic polyoxometalate
- special reaction equipment and special reaction conditions of high temperature and high pressure are necessary.
- glycolic acid obtained using reaction conditions of high temperature and high pressure contains a large amount of various impurities.
- the method (2) of reacting formaldehyde with hydrogen cyanide requires the use of an extremely poisonous starting raw material, i.e., hydrogen cyanide.
- the method (3) of reacting monochloroacetic acid with sodium hydroxide requires use of an about stoichiometric amount of sodium hydroxide.
- One problem is that sodium chloride generated raises the slurry concentration, leading to poor operability.
- Another problem is that this salt cannot be removed completely and remains in the product.
- ethylene glycol is produced from fossil-based feedstocks.
- ethylene glycol can be produced using ethylene oxide as a raw material.
- the step of producing ethylene glycol is long and in addition, ethylene oxide, which is explosive, must be well handled in the production process.
- glycolic acid obtained by these methods utilize fossil-based feedstocks.
- PCT. Pub. No. WO2018/095973 teaches a method for preparing glycolic acid from glycolaldehyde in the presence of a metal-based catalyst.
- Said metal-based catalyst is selected from the group consisting of Pt, Pd and mixtures thereof.
- Pt, Pd and mixtures thereof are selected from the group consisting of Pt, Pd and mixtures thereof.
- high catalyst to substrate loading is necessary according to Example 1.
- the supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support is more active than the metal catalysts used in prior art.
- the selectivity and the yield to glycolic acid can be well improved by using this kind of supported catalyst.
- high catalyst to substrate loading is not necessary in the reaction.
- the catalyst is more stable at oxygen rich conditions.
- the present invention therefore pertains to a method for preparing glycolic acid comprising oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- the invention also concerns a mixture comprising glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.
- Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
- Glycolaldehyde subject to molecular oxygen oxidation can be a bio-based raw material.
- Bio-based raw material refers to a product consisting of a substance, or substances, originally derived from living organisms. These substances may be natural or synthesized organic compounds that exist in nature.
- glycolaldehyde can be produced by high-temperature fragmentation of carbohydrates to produce a mixture of C 1 -C 3 oxygenates such as described in U.S. Pat. No. 7,094,932, U.S. Pat. No. 5,397,582 and WO 2017/216311.
- the carbohydrate used for thermal fragmentation to provide a C 1 -C 3 oxygenate mixture may be mono-and/or disaccharide.
- the mono-and/or di-saccharide is selected from the group consisting of sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose and fructose; or mixtures thereof.
- the monosaccharide is selected from the group consisting of glucose, galactose, tagatose, mannose, fructose, xylose, arabinose, ribose; or mixtures thereof.
- molecular oxygen is a diatomic molecule that is composed of two oxygen atoms held together by a covalent bond.
- molecular oxygen is supplied in the form of oxygen gas.
- the purity of oxygen gas is of at least 99%.
- the oxidation reaction is performed at an O 2 partial pressure which is advantageously in the range of 1 to 10 bar in this embodiment.
- molecular oxygen is supplied in the form of air.
- the oxidation reaction is performed at an air partial pressure which is advantageously in the range of 0.15 to 1 bar in this embodiment.
- the reaction may be carried out in a batch type reactor or in a continuous type reactor.
- the molar ratio of molecular oxygen to glycoaldehyde preferably ranges from 1 to 10 mol/mol.
- the molecular oxygen flow rate preferably ranges from 0.1 to 0.5 L/min.
- the noble metal in the supported catalyst is selected from the group consisting of Pt, Pd, Ru and Rh.
- the noble metal is Pt.
- the support to the metal catalyst is not particularly limited. It can notably be a metal oxide chosen in the group consisting of aluminum oxide (Al 2 O 3 ) , silicon dioxide (SiO 2 ) , titanium oxide (TiO 2 ) , zirconium dioxide (ZrO 2 ) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La 2 O 3 ) , niobium dioxide (NbO 2 ) , cerium oxide (CeO 2 ) and mixtures thereof.
- Al 2 O 3 aluminum oxide
- SiO 2 silicon dioxide
- TiO 2 titanium oxide
- ZrO 2 zirconium dioxide
- CaO calcium oxide
- MgO magnesium oxide
- La 2 O 3 lanthanum oxide
- NbO 2 niobium dioxide
- CeO 2 cerium oxide
- the support can also be a zeolite.
- Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.
- the support of catalyst can even be Kieselguhr, clay or carbon.
- the support is carbon or aluminum oxide (Al 2 O 3 ) . More preferably, the support is carbon.
- the loading of the noble metal ranges from 1 to 10 wt. %based on total weight of catalyst and preferably from 3 to 5 wt. %.
- the weight ratio of Bi to the noble metal in the supported catalyst preferably ranges from 0.03 to 1 and more preferably from 0.2 to 0.3.
- the supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support has better catalytic activity.
- the loading of catalyst to substrate can be lower than prior art to achieve the same performance.
- Preferable weight ratio of the supported catalyst to glycolaldehyde is from 5 to 50 %and more preferably from 5 to 10 %.
- the supported catalysts used in the method according to the present invention include those commercially available, such as Pt-Bi/C from Johnson Matthey.
- the solvent used in the method according to the present invention can be water, ether, methanol or ethanol.
- Preferable solvent is water.
- the method according to the present invention comprises the following steps:
- the proper temperature can be preferably from 20 to 120°C.
- the proper time can be preferably from 0.25h to 25h.
- the invention also concerns a mixture comprising glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- glycolaldehyde 2.0 mL of water and 25 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a stainless-steel autoclave with a Teflon insert.
- the autoclave was closed and charged with 10 bar of oxygen.
- the autoclave was heated to 80°C, stirred using a magnetic stir bar and held for 6 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 97%and the yield to glycolic acid was 78%.
- glycolaldehyde 1.5 mL of water and 50 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a stainless-steel autoclave with a Teflon insert.
- the autoclave was closed and charged with 10 bar of oxygen.
- the autoclave was heated to 30°C, stirred using a magnetic stir bar and held for 24 hours. After reaction, the products were analyzed by HPLC.
- the conversion of glycolaldehyde was 83%and the yield to glycolic acid was 74%.
- glycolaldehyde 1.5 mL of water and 50 mg of 5wt. %Pt/C catalyst were added to a stainless-steel autoclave with a Teflon insert.
- the autoclave was closed and charged with 10 bar of oxygen.
- the autoclave was heated to 30°C, stirred using a magnetic stir bar and held for 24 hours. After reaction, the products were analyzed by HPLC.
- the conversion of glycolaldehyde was 72%and the yield to glycolic acid was 56%.
- glycolaldehyde 480 mg of glycolaldehyde, 4.0 mL of water and 50 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a glass flask with a condenser. Air was bubbled through the liquid mixture at 0.1 L/min. The glass flask was heated to 60°C and held for 7 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 82%and the yield to glycolic acid was 71%.
- glycolaldehyde 480 mg of glycolaldehyde, 4.0 mL of water and 150 mg of 5wt. %Pt/C catalyst were added to a glass flask with a condenser. Air was bubbled through the liquid mixture at 0.1 L/min. The glass flask was heated to 60°C and held for 7 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 18%and the yield to glycolic acid was 16%.
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Abstract
Provided is a method for preparing glycolic acid which comprises oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst. Said supported catalyst comprises (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support. Advantageously, the supported metallic catalyst is more active than the catalysts used in prior art. Furthermore, the catalyst is more stable at oxygen rich conditions.
Description
The present invention relates to a method for preparing glycolic acid comprising oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
Glycolic acid has conventionally been used mainly as boiler compounds, cleaning agents, leather tanning agents, chelating agents of metal ions and the like. In recent years, its applications have expanded to cosmetics, personal care and pharmaceuticals for external use. Glycolic acid to be used for pharmaceuticals requires high purity grade and is desired to contain a lower level of harmful impurities. Glycolic acid has recently been expected also as a raw material for polyglycolic acid having biodegradability and a gas barrier function.
Typical examples of a conventionally known method for producing glycolic acid include (1) a method of reacting carbon monoxide, formaldehyde and water in the presence of a strongly acidic catalyst under high-temperature and high-pressure conditions, (2) a method of reacting formaldehyde with hydrogen cyanide, (3) a method of reacting chloroacetic acid with sodium hydroxide, (4) a method of carrying out a Cannizzaro reaction between glyoxal available by oxidation of ethylene glycol and a strong alkali to form a glycolate salt, and then adding an acid to liberate glycolic acid from the resulting glycolate salt; (5) a method of carrying out a liquid-phase reaction between glyoxal available by oxidation of ethylene glycol and water in the presence of an inorganic catalyst; (6) a method for catalytic oxidation of ethylene glycol in the presence of a noble metal catalyst and oxygen; and (7) a method of carrying out oxidative esterification of ethylene glycol with methanol and oxygen to obtain methyl glycolate and then hydrolyzing into glycolic acid.
The method (1) is performed in the presence of a strongly acidic catalyst such as acidic polyoxometalate under high-temperature and high-pressure conditions. Thus, special reaction equipment and special reaction conditions of high temperature and high pressure are necessary. At the same time, glycolic acid obtained using reaction conditions of high temperature and high pressure contains a large amount of various impurities.
The method (2) of reacting formaldehyde with hydrogen cyanide requires the use of an extremely poisonous starting raw material, i.e., hydrogen cyanide.
The method (3) of reacting monochloroacetic acid with sodium hydroxide requires use of an about stoichiometric amount of sodium hydroxide. One problem is that sodium chloride generated raises the slurry concentration, leading to poor operability. Another problem is that this salt cannot be removed completely and remains in the product.
A problem common to the methods (4) to (7) is that ethylene glycol is produced from fossil-based feedstocks. For example, ethylene glycol can be produced using ethylene oxide as a raw material. The step of producing ethylene glycol is long and in addition, ethylene oxide, which is explosive, must be well handled in the production process.
As reported by Electrochimica Acta (1994) , 39 (11-12) , 1877-80, previous efforts to oxidize glycolaldehyde have shown that the primary product from the electrochemical oxidation of glycolaldehyde over Pt electrodes is glyoxal, with only minor production of glycolic acid. Electrochemical modification of the electrode surface by deposition of an ad-atom layer of Bi was necessary to shift the selectivity to glycolic acid; a process which is not easily translated into industrial production.
The conventional production methods have the above-described drawbacks. In particular, glycolic acid obtained by these methods utilize fossil-based feedstocks.
U.S. Pub. No. 2013/0281733 reports glycolaldehyde was oxidized to glycolic acid using 0.5 MPa O
2 at 180 ℃ in the presence of a molybdenum-containing acidic catalysts. Glycolaldehyde in this case was an intermediate in cellulose oxidation. The yield of glycolic acid obtained by this method is low.
PCT. Pub. No. WO2018/095973 teaches a method for preparing glycolic acid from glycolaldehyde in the presence of a metal-based catalyst. Said metal-based catalyst is selected from the group consisting of Pt, Pd and mixtures thereof. However, due to the poor activity of this catalyst, high catalyst to substrate loading is necessary according to Example 1.
There is still a need to develop an industrially applicable process to prepare glycolic acid with a high yield and selectivity based on inexpensive and sustainable feedstocks, such as bio-based materials with desired characteristics such as low cost, simple equipment, mild reaction conditions, ease of handle, which can overcome the drawbacks in prior arts. Specifically, the inventors have now found that the supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support is more active than the metal catalysts used in prior art. Thus, the selectivity and the yield to glycolic acid can be well improved by using this kind of supported catalyst. Meanwhile, high catalyst to substrate loading is not necessary in the reaction. Furthermore, the catalyst is more stable at oxygen rich conditions.
SUMMARY OF THE INVENTION
The present invention therefore pertains to a method for preparing glycolic acid comprising oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
The invention also concerns a mixture comprising glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
DEFINITIONS
Throughout the description, including the claims, the term ″comprising one″ should be understood as being synonymous with the term ″comprising at least one″ , unless otherwise specified, and ″between″ should be understood as being inclusive of the limits.
As used herein, the terminology ″ (C
n-C
m) ″ in reference to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.
The articles “a” , “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
The term “and/or” includes the meanings “and” , “or” and also all the other possible combinations of the elements connected to this term.
It is specified that, in the continuation of the description, unless otherwise indicated, the values at the limits are included in the ranges of values which are given.
Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
DETAILS OF THE INVENTION
Glycolaldehyde subject to molecular oxygen oxidation can be a bio-based raw material. Bio-based raw material refers to a product consisting of a substance, or substances, originally derived from living organisms. These substances may be natural or synthesized organic compounds that exist in nature. For example, it is known that glycolaldehyde can be produced by high-temperature fragmentation of carbohydrates to produce a mixture of C
1-C
3 oxygenates such as described in U.S. Pat. No. 7,094,932, U.S. Pat. No. 5,397,582 and WO 2017/216311.
The carbohydrate used for thermal fragmentation to provide a C
1-C
3 oxygenate mixture may be mono-and/or disaccharide. In an embodiment, the mono-and/or di-saccharide is selected from the group consisting of sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose and fructose; or mixtures thereof. In a further embodiment, the monosaccharide is selected from the group consisting of glucose, galactose, tagatose, mannose, fructose, xylose, arabinose, ribose; or mixtures thereof.
As used herein, molecular oxygen is a diatomic molecule that is composed of two oxygen atoms held together by a covalent bond.
In one embodiment, molecular oxygen is supplied in the form of oxygen gas. Preferably, the purity of oxygen gas is of at least 99%. The oxidation reaction is performed at an O
2 partial pressure which is advantageously in the range of 1 to 10 bar in this embodiment.
In another embodiment, molecular oxygen is supplied in the form of air. The oxidation reaction is performed at an air partial pressure which is advantageously in the range of 0.15 to 1 bar in this embodiment.
The reaction may be carried out in a batch type reactor or in a continuous type reactor. In batch type reactor, the molar ratio of molecular oxygen to glycoaldehyde preferably ranges from 1 to 10 mol/mol. In continuous type reactor, the molecular oxygen flow rate preferably ranges from 0.1 to 0.5 L/min.
The noble metal in the supported catalyst is selected from the group consisting of Pt, Pd, Ru and Rh. Preferably, the noble metal is Pt.
The support to the metal catalyst is not particularly limited. It can notably be a metal oxide chosen in the group consisting of aluminum oxide (Al
2O
3) , silicon dioxide (SiO
2) , titanium oxide (TiO
2) , zirconium dioxide (ZrO
2) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La
2O
3) , niobium dioxide (NbO
2) , cerium oxide (CeO
2) and mixtures thereof.
The support can also be a zeolite. Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.
The support of catalyst can even be Kieselguhr, clay or carbon.
Preferably, the support is carbon or aluminum oxide (Al
2O
3) . More preferably, the support is carbon.
The loading of the noble metal ranges from 1 to 10 wt. %based on total weight of catalyst and preferably from 3 to 5 wt. %.
The weight ratio of Bi to the noble metal in the supported catalyst preferably ranges from 0.03 to 1 and more preferably from 0.2 to 0.3.
It was surprisingly found that the supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support has better catalytic activity. Thus, the loading of catalyst to substrate can be lower than prior art to achieve the same performance. Preferable weight ratio of the supported catalyst to glycolaldehyde is from 5 to 50 %and more preferably from 5 to 10 %.
The supported catalysts used in the method according to the present invention include those commercially available, such as Pt-Bi/C from Johnson Matthey.
The solvent used in the method according to the present invention can be water, ether, methanol or ethanol. Preferable solvent is water.
The method according to the present invention comprises the following steps:
(i) Mixing glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support;
(ii) Heating the mixture obtained at step (i) at proper temperature for proper time to prepare glycolic acid.
The proper temperature can be preferably from 20 to 120℃.
The proper time can be preferably from 0.25h to 25h.
The invention also concerns a mixture comprising glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
The following examples are included to illustrate embodiments of the invention. Needless to say, the invention is not limited to described examples.
EXPERIMENTAL PART
Materials
- Glycolaldehyde Dimer, CAS No. 23147-58-2, purity > 95%from Adamas-beta
- 5%Pt-1.5%Bi/C, Type 160, CAS No. 7440-06-4, Johnson Matthey
- 5%Pt/C, CAS No. 7440-06-4, Johnson Matthey
Example 1
240 mg of glycolaldehyde, 2.0 mL of water and 25 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a stainless-steel autoclave with a Teflon insert. The autoclave was closed and charged with 10 bar of oxygen. The autoclave was heated to 80℃, stirred using a magnetic stir bar and held for 6 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 97%and the yield to glycolic acid was 78%.
Example 2
240 mg of glycolaldehyde, 1.5 mL of water and 50 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a stainless-steel autoclave with a Teflon insert. The autoclave was closed and charged with 10 bar of oxygen. The autoclave was heated to 30℃, stirred using a magnetic stir bar and held for 24 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 83%and the yield to glycolic acid was 74%.
Example 3
240 mg of glycolaldehyde, 1.5 mL of water and 50 mg of 5wt. %Pt/C catalyst were added to a stainless-steel autoclave with a Teflon insert. The autoclave was closed and charged with 10 bar of oxygen. The autoclave was heated to 30℃, stirred using a magnetic stir bar and held for 24 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 72%and the yield to glycolic acid was 56%.
Example 4
480 mg of glycolaldehyde, 4.0 mL of water and 50 mg of 5wt. %Pt-1.5wt. %Bi/C catalyst were added to a glass flask with a condenser. Air was bubbled through the liquid mixture at 0.1 L/min. The glass flask was heated to 60℃ and held for 7 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 82%and the yield to glycolic acid was 71%.
Example 5
480 mg of glycolaldehyde, 4.0 mL of water and 150 mg of 5wt. %Pt/C catalyst were added to a glass flask with a condenser. Air was bubbled through the liquid mixture at 0.1 L/min. The glass flask was heated to 60℃ and held for 7 hours. After reaction, the products were analyzed by HPLC. The conversion of glycolaldehyde was 18%and the yield to glycolic acid was 16%.
Claims (16)
- A method for preparing glycolic acid comprising oxidizing glycolaldehyde with molecular oxygen in the presence of a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- The method according to claim 1, wherein the weight ratio of Bi to the noble metal in the supported catalyst ranges from 0.03 to 1.
- The method according to claim 2, wherein the weight ratio of Bi to the noble metal in the supported catalyst ranges from 0.2 to 0.3.
- The method according to any one of claims 1-3, wherein the loading of the noble metal ranges from 1 to 10 wt. % based on total weight of catalyst.
- The method according to claim 4, wherein the loading of the noble metal ranges from 3 to 5 wt. % based on total weight of catalyst.
- The method according to any one of claims 1-5, wherein the weight ratio of the supported catalyst to glycolaldehyde is from 5 to 50 %.
- The method according to claim 6, wherein the weight ratio of the supported catalyst to glycolaldehyde is from 5 to 10 %.
- The method according to any one of claims 1-7, wherein the noble metal is Pt.
- The method according to any one of claims 1-8, wherein the support is carbon or aluminum oxide.
- The method according to any one of claims 1-9, wherein molecular oxygen is supplied in the form of oxygen gas or air.
- The method according to claim 10, wherein molecular oxygen is supplied in the form of oxygen gas having a purity of at least 99%.
- A mixture comprising glycolaldehyde, molecular oxygen, a solvent and a supported catalyst comprising (i) a noble metal selected from the group consisting of Pt, Pd, Ru and Rh, (ii) Bi and (iii) a support.
- The mixture according to claim 12, wherein molecular oxygen is in the form of oxygen gas having a purity of at least 99%.
- The mixture according to claim 12 or 13, wherein the solvent is water.
- The mixture according to any one of claims 12 to 14, wherein the noble metal is Pt.
- The mixture according to any one of claims 12 to 14, wherein the support is carbon.
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CN201980097241.3A CN113950468A (en) | 2019-06-27 | 2019-06-27 | Method for producing glycolic acid |
US17/610,761 US20220306563A1 (en) | 2019-06-27 | 2019-06-27 | Method for preparing glycolic acid |
JP2021569959A JP7389822B2 (en) | 2019-06-27 | 2019-06-27 | How to prepare glycolic acid |
EP19935745.0A EP3953320A4 (en) | 2019-06-27 | 2019-06-27 | Method for preparing glycolic acid |
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JP2006117576A (en) * | 2004-10-20 | 2006-05-11 | Toho Chem Ind Co Ltd | Process of glycolic acid |
EP1894910A1 (en) * | 2005-05-27 | 2008-03-05 | Asahi Kasei Chemicals Corporation | Method for producing glycolic acid |
WO2009140787A1 (en) * | 2008-05-20 | 2009-11-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for production of glycolic acid |
WO2018051115A1 (en) * | 2016-09-16 | 2018-03-22 | Johnson Matthey Davy Technologies Limited | Process for the production of glycolic acid |
US20180086686A1 (en) * | 2015-04-08 | 2018-03-29 | Johnson Matthey Davy Technologies Limited | Process for the production of glycolic acid |
WO2018095973A1 (en) * | 2016-11-24 | 2018-05-31 | Haldor Topsøe A/S | A method and a system for producing glycolic acid and/or glycolate |
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JP2006117576A (en) * | 2004-10-20 | 2006-05-11 | Toho Chem Ind Co Ltd | Process of glycolic acid |
EP1894910A1 (en) * | 2005-05-27 | 2008-03-05 | Asahi Kasei Chemicals Corporation | Method for producing glycolic acid |
WO2009140787A1 (en) * | 2008-05-20 | 2009-11-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for production of glycolic acid |
US20180086686A1 (en) * | 2015-04-08 | 2018-03-29 | Johnson Matthey Davy Technologies Limited | Process for the production of glycolic acid |
WO2018051115A1 (en) * | 2016-09-16 | 2018-03-22 | Johnson Matthey Davy Technologies Limited | Process for the production of glycolic acid |
WO2018095973A1 (en) * | 2016-11-24 | 2018-05-31 | Haldor Topsøe A/S | A method and a system for producing glycolic acid and/or glycolate |
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