CN107445833A - The method of ethyl glycolate oxidation synthesis glyoxylate ester - Google Patents
The method of ethyl glycolate oxidation synthesis glyoxylate ester Download PDFInfo
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- CN107445833A CN107445833A CN201610368005.9A CN201610368005A CN107445833A CN 107445833 A CN107445833 A CN 107445833A CN 201610368005 A CN201610368005 A CN 201610368005A CN 107445833 A CN107445833 A CN 107445833A
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- Prior art keywords
- ethyl glycolate
- catalyst
- oxidation synthesis
- slurry
- ester according
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- 238000000034 method Methods 0.000 title claims abstract description 44
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- -1 glyoxylate ester Chemical class 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- DBPFRRFGLYGEJI-UHFFFAOYSA-N ethyl glyoxylate Chemical compound CCOC(=O)C=O DBPFRRFGLYGEJI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002796 Si–Al Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 74
- 239000000243 solution Substances 0.000 description 73
- 238000003756 stirring Methods 0.000 description 58
- 239000012065 filter cake Substances 0.000 description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 46
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 46
- 238000001035 drying Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 30
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 description 25
- 230000032683 aging Effects 0.000 description 24
- 238000003483 aging Methods 0.000 description 23
- 238000012512 characterization method Methods 0.000 description 23
- 238000001914 filtration Methods 0.000 description 21
- 238000007598 dipping method Methods 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 15
- 239000011591 potassium Substances 0.000 description 15
- 239000004323 potassium nitrate Substances 0.000 description 14
- 235000010333 potassium nitrate Nutrition 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 11
- 238000009472 formulation Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- KFKXSMSQHIOMSO-UHFFFAOYSA-N methyl 2-oxoacetate Chemical class COC(=O)C=O KFKXSMSQHIOMSO-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229960000458 allantoin Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940124585 oral penicillin Drugs 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7207—A-type
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of ethyl glycolate oxidation synthesis glyoxylate ester, mainly solve the problems, such as to have glyoxylic ester in the prior art selectively low.The present invention is by using including making oxygen-containing gas and ethyl glycolate contact the reactions steps of generation glyoxylic ester in the presence of a catalyst；The catalyst is in terms of parts by weight, including following component：A) at least one of 0.5~30 part oxide selected from iron or iron active constituent；B) 0~10 part is selected from least one of IA or Group IIA metal or oxides additive；C) technical scheme of 70~99 parts of carrier preferably solves the problem, in the industrial production that glyoxylic ester processed is aoxidized available for ethyl glycolate.
Description
Technical field
The present invention relates to a kind of method of ethyl glycolate oxidation synthesis glyoxylate ester.
Background technology
Glyoxylic ester has the chemical property of aldehyde and ester concurrently, and a variety of reactions can occur, and particularly hydrolysis can prepare glyoxalic acid.
And glyoxalic acid is the organic intermediates such as synthetic perfume, medicine, food, varnish raw material, dyestuff, plastic additive, available for producing
Oral penicillin, vanillic aldehyde, mandelic acid and allantoin etc., so both at home and abroad to the consumption figure of glyoxalic acid also becoming into rising always
Gesture.
Process for production of glyoxalic acid is different by initiation material, and it is as many as several to there are about ten at present.Industrial the most frequently used have oxalic acid
Electrolytic reduction, glyoxal nitric acid oxidation method, maleic acid (acid anhydride) ozonization method etc..Current domestic glyoxalic acid industry run into two compared with
The problem of big：First, it is high-volume, the glyoxalic acid insufficient supply of high quality, prevents the price advantage of product downstream from abundant
Play, the serious market development that have impact on glyoxalic acid and its downstream product；Secondly, it is domestic substantially all using glyoxal method
Produce glyoxalic acid.And the fluctuation of International Crude Oil, the price of glyoxal is influenceed, it is final to influence glyoxalic acid price.
China has abundant coal, natural gas resource, and petroleum resources are insufficient, so opening up the side of Non oil-based route
Method, there is its own strategic significance in China.In the 1970s, being influenceed by world oil crisis, various countries start to carry out one after another
Largely the C1 chemical research based on natural gas and coal-based feedstocks, correlation technique also achieve quickly in the nineties in last century
Development, especially achieve great breakthrough, thing followed meeting in terms of research produces ethylene glycol using coal or natural gas as raw material
Substantial amounts of process byproducts ethyl glycolate is produced, so the Non oil-based route that exploitation aoxidizes glyoxylic ester processed with ethyl glycolate has
Very high competitiveness.
But it is that the first order in whole oxidation reaction process is anti-by the reaction of ethyl glycolate oxidation synthesis glyoxylate ester
Should, if continuing to walk downward can make glyoxalic acid methylester be further oxidized to acid, further aoxidize, can produce substantial amounts of a large amount of
Carbon dioxide and water, the two reactions can all cause the reduction of glyoxylic ester yield；And due to this oxidation reaction need 200~
400 DEG C could obtain higher ethyl glycolate conversion ratio, also easily make oxidation reaction excessive under this condition, so having to
The yield for improving glyoxylic ester using higher catalyst is reacted stair oxidation.But just both at home and abroad at present to such reaction
Report that the yield of glyoxylic ester is not high.For example, document US4340748 disclose it is a kind of using ethyl glycolate as raw material 100~
Catalytic gas phase oxidation is carried out to it with oxygen-containing gas under the conditions of 600 DEG C, preferably 200~400 DEG C and obtains the method for glyoxylic ester, but
It is that catalyst used in this method is relatively low to the yield of glyoxylic ester, below 88.3%, glyoxalic acid under the conditions of some
The yield of ester only has 43.5%.
The content of the invention
The technical problems to be solved by the invention are that prior art has the selection of ethyl glycolate oxidative dehydrogenation glyoxylic ester
A kind of the problem of property is low, there is provided method of new ethyl glycolate oxidation synthesis glyoxylate ester.This method has glyoxylic ester selection
The characteristics of property is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of ethyl glycolate oxidative synthesis acetaldehyde
The method of acid esters, including the reactions steps for making oxygen-containing gas and ethyl glycolate contact generation glyoxylic ester in the presence of a catalyst；
The catalyst is in terms of parts by weight, including following component：
A) at least one of 0.5~30 part oxide selected from iron or iron active constituent；
B) 0~10 part is selected from least one of IA or Group IIA metal or oxides additive；
C) 70~99 parts of carrier.
In above-mentioned technical proposal, in terms of parts by weight, the dosage of active constituent is 2~25 parts, and the dosage of auxiliary agent is 0.05
~7 parts, the dosage of carrier is 73~97.9 parts.
In above-mentioned technical proposal, the carrier is in silica, aluminum oxide, zirconium oxide, titanium oxide or Si-Al molecular sieve
At least one.Preferably, the carrier is selected from least one of aluminum oxide, zirconium oxide or titanium oxide.
In above-mentioned technical proposal, the specific surface area of catalyst is 15~700 meters2/ gram.Preferably, the catalyst ratio
Surface area is 50~500 meters2/ gram.
In above-mentioned technical proposal, reaction condition includes：200~450 DEG C, 0~1.5MPa of reaction pressure of reaction temperature, during liquid
Weight space velocity is 0.1~1.5 hour-1, in oxygen-containing gas it is oxygenous with the mol ratio of ethyl glycolate (0.5~2):1.It is preferred that
Ground, 230~400 DEG C, 0~1.0MPa of reaction pressure of reaction temperature, weight space velocity is 0.2~1.0 hour during liquid-1, oxygen-containing gas
It is middle oxygenous with the mol ratio of ethyl glycolate (0.6~1.5):1.
In above-mentioned technical proposal, the nitrogen that 0.5~10 times of volume of oxygen-containing gas is added in raw material is Balance Air.
In above-mentioned technical proposal, the glyoxylic ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
The preparation method of catalyst described in the inventive method comprises the following steps：
1) active constituent a) soluble-salt is made into mixed solution I；
2) carrier is added in solution I under stirring, obtains slurry II；
3) will be configured to selected from least one of carbonate, bicarbonate, the hydroxide of alkali metal or inorganic ammoniacal liquor
Solution III makees precipitating reagent；
4) solution III is mixed with slurry II, the pH value of precipitation reaction terminal is 5.6~12, obtains slurry IV；
5) filter, wash after slurry IV is aged, obtain filter cake V；
6) by filter cake V in 60~130 DEG C of drying；
7) component b) soluble-salt is made into mixed solution VI, then by the incipient impregnation of solution VI in filter cake V；
8) 60~130 DEG C of drying of filter cake that will have been impregnated, 300~600 DEG C of roastings obtain the catalyst.
In above-mentioned technical proposal, active constituent a) soluble-salt in nitrate, acetate or oxalates at least
It is a kind of.Carbonate or bicarbonate in precipitating reagent are preferably selected from the carbonate or bicarbonate of alkali metal or alkaline-earth metal
At least one；The hydroxide of alkali metal is preferably selected from least one of sodium hydroxide or potassium hydroxide；Inorganic ammonia is excellent
Elect as and be selected from least one of liquefied ammonia or ammoniacal liquor.The pH value of precipitation reaction terminal is preferably 7~11 in step 4).In step 5)
The Aging Temperature of slurry IV is preferably 50~100 DEG C, and digestion time is preferably 3~48 hours.
The reaction of ethyl glycolate oxidation synthesis glyoxylate ester is the first order reaction in whole oxidation reaction process, if after
Continuous walk downward can make glyoxalic acid methylester be further oxidized to acid, further aoxidize, can produce substantial amounts of great amount of carbon dioxide and
Water, the two reactions can all cause the reduction of glyoxylic ester yield.And the temperature of this reaction is higher, generally 200~400
DEG C higher ethyl glycolate conversion ratio could be obtained, over oxidation easily occurs under this condition, produces substantial amounts of titanium dioxide
Carbon and water.By the present invention in that being main active component and the auxiliary agent synergy of addition with iron, reaction is set to rest on stair oxidation
Reaction, improve the yield of glyoxylic ester.Using the inventive method, glyoxylic ester selectively can reach 95%, achieve compared with
Good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The solution I for preparing the ferric nitrate of 200ml iron content 5.6% simultaneously stirs, and than surface is 105m by 100g2/ g carrying aluminas
Body adds solution I and stirred, and obtains slurry II, then ammoniacal liquor is added drop-wise in slurry II under stirring, controls terminal
PH is 8 to obtain slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then washs filter cake with ethanol and deionized water, 120 DEG C
Drying.Filter cake after potassium nitrate solution dippings of the 50ml containing potassium 2.3% is dried, 120 DEG C of drying are prepared again, and 500 DEG C of roastings are urged
Agent C1, catalyst sample is taken to do X- fluorescence (XRF) measure catalytic component, and than surface BET characterization tests, test result
It is shown in Table 1.
【Embodiment 2】
Press【Embodiment 1】Method prepare 200ml iron content 12.8% ferric nitrate solution I and stir, 100g is compared into table
Face is 20m2/ g Zirconia carriers add solution I and stirred, and obtain slurry II, are then added drop-wise to ammoniacal liquor under stirring
In slurry II, it is 8 to control terminal pH, obtains slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and go from
Sub- water washing filter cake, 120 DEG C of drying.Filter cake after magnesium nitrate solution dippings of the 40ml containing magnesium 4.8% is dried, 120 DEG C of bakings are prepared again
Dry, 500 DEG C of roastings obtain catalyst C2, take catalyst sample to do caesium XRF and BET characterization test, test result is shown in Table 1.
【Embodiment 3】
Press【Embodiment 1】Method prepare 200ml iron content 2.9% ferric nitrate solution I and stir, 100g is compared into surface
For 250m2/ g alumina supports add solution I and stirred, and obtain slurry II, are then added drop-wise to ammoniacal liquor under stirring
In slurry II, it is 8 to control terminal pH, obtains slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and go from
Sub- water washing filter cake, 120 DEG C of drying.Filter cake after sodium nitrate solution dippings of the 50ml containing sodium 15.9% is dried, 120 DEG C of bakings are prepared again
Dry, 500 DEG C of roastings obtain catalyst C3, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 4】
Press【Embodiment 1】Method prepare 200ml iron content 5.6% ferric nitrate solution I and stir, 100g is compared into surface
For 105m2/ g alumina supports add solution I and stirred, and obtain slurry II, are then added drop-wise to ammoniacal liquor under stirring
In slurry II, terminal pH is controlled to obtain slurry IV for 8, product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and deionization
Water washing filter cake, 120 DEG C of drying.Filter cake after cesium nitrate solution dippings of the 50ml containing caesium 2.25% is dried, 120 DEG C of bakings are prepared again
Dry, 500 DEG C of roastings obtain catalyst C4, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 5】
Press【Embodiment 1】Method prepare 200ml iron content 1% ferric nitrate solution I and stir, be than surface by 100g
395m2/ g silica supports add solution I and stirred, and obtain slurry II, ammoniacal liquor then is added drop-wise into slurry under stirring
In material II, it is 8 control terminal pH, obtains slurry IV, and 80 DEG C of ageings are taken out product after 5 hours and filtered, then with ethanol and deionization
Water washing filter cake, 120 DEG C of drying.The calcium nitrate solution for preparing 100ml calcics 1% again impregnates filter cake after drying, and 120 DEG C dry,
500 DEG C of roastings obtain catalyst C5, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 6】
Press【Embodiment 1】Method prepare 200ml iron content 16.68% ferric nitrate solution I and stir, 100g is compared into table
Face is 94m2/ g titanium dioxide carriers add solution I and stirred, and obtain slurry II, are then added drop-wise to ammoniacal liquor under stirring
In slurry II, it is 8 to control terminal pH, obtains slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and go from
Sub- water washing filter cake, 120 DEG C of drying.Filter cake after liquor kalii acetici dippings of the 40ml containing potassium 0.17% is dried, 120 DEG C of bakings are prepared again
Dry, 500 DEG C of roastings obtain catalyst C6, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 7】
Press【Embodiment 1】Method prepare 200ml iron content 0.25% ferric nitrate solution I and stir, 100g is compared into table
Face is 105m2/ g alumina supports add solution I and stirred, and obtain slurry II, then ammoniacal liquor is added dropwise under stirring
Into slurry II, it is 8 to control terminal pH, obtains slurry IV, and 80 DEG C of ageings take out product filtering after 5 hours, then with ethanol and go
Ion water washing filter cake, 120 DEG C of drying.Filter cake after magnesium nitrate solution dippings of the 50ml containing magnesium 2% is dried, 120 DEG C of bakings are prepared again
Dry, 500 DEG C of roastings obtain catalyst C7, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 8】
Press【Embodiment 1】Method prepare 200ml iron content 22% ferric nitrate solution I and stir, 100g is compared into surface
For 105m2/ g alumina supports add solution I and stirred, and obtain slurry II, are then added drop-wise to ammoniacal liquor under stirring
In slurry II, it is 8 to control terminal pH, obtains slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and go from
Sub- water washing filter cake, 120 DEG C of drying.The barium nitrate solution for preparing 50ml barics 8.96% again impregnates filter cake after drying, 120 DEG C of bakings
Dry, 500 DEG C of roastings obtain catalyst C8, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 9】
Press【Embodiment 1】Method prepare 200ml iron content 9% ferric nitrate solution I and stir, be than surface by 100g
105m2/ g alumina supports add solution I and stirred, and obtain slurry II, ammoniacal liquor then is added drop-wise into slurry under stirring
In material II, it is 8 control terminal pH, obtains slurry IV, and 80 DEG C of ageings are taken out product after 5 hours and filtered, then with ethanol and deionization
Water washing filter cake, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C9, take catalyst sample to do XRF and BET characterization tests, survey
Test result is shown in Table 1.
【Embodiment 10】
Press【Embodiment 1】Method prepare 200ml iron content 10% ferric nitrate solution I and stir, 100g is compared into surface
For 690m2/ g 3A types molecular sieve carrier adds solution I and stirred, and obtains slurry II, then drips ammoniacal liquor under stirring
Be added in slurry II, it is 8 to control terminal pH, obtains slurry IV, and product filtering is taken out in 80 DEG C of ageings after 5 hours, then with ethanol and
Deionized water washs filter cake, 120 DEG C of drying.Prepare again 80ml containing magnesium 17% magnesium nitrate solution dipping drying after filter cake, 120 DEG C
Drying, 500 DEG C of roastings obtain catalyst C10, take catalyst sample to do XRF and BET characterization tests, test result is shown in Table 1.
【Embodiment 11】
Press【Embodiment 1】Method, simply change the aluminum oxide trade mark.Prepare the solution of the ferric nitrate of 200ml iron content 5.6%
I and stir, than surface be 721m by 100g2/ g alumina supports add solution I and stirred, and obtain slurry II, are then stirring
Mix and ammoniacal liquor is added drop-wise in slurry II under state, it is 8 to control terminal pH, obtains slurry IV, and 80 DEG C of ageings take out product after 5 hours
Filtering, then wash filter cake, 120 DEG C of drying with ethanol and deionized water.Potassium nitrate solution dippings of the 50ml containing potassium 2.3% is prepared again
Filter cake after drying, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C11, take catalyst sample to do XRF and BET characterization tests, survey
Test result is shown in Table 1.
【Embodiment 12】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index, i.e.,：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface will be 105m by 100g2/ alumina support add solution I stir
Uniformly, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, controls terminal pH to obtain slurry for 5.6
IV, 80 DEG C of ageings take out product filtering after 5 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.Prepare again
Filter cake after potassium nitrate solution dipping drying of the 50ml containing potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C12, take and urge
Agent sample does XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 13】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 12 to control terminal pH, obtains slurry IV,
80 DEG C of ageings take out product filtering after 5 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again to contain
Filter cake after the potassium nitrate solution dipping drying of potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C13, take catalyst sample
Product do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 14】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 7 to control terminal pH, obtains slurry IV,
80 DEG C of ageings take out product filtering after 5 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again to contain
Filter cake after the potassium nitrate solution dipping drying of potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C14, take catalyst sample
Product do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 15】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, controls terminal pH to obtain slurry IV for 11,
80 DEG C of ageings take out product filtering after 5 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again to contain
Filter cake after the potassium nitrate solution dipping drying of potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C15, take catalyst sample
Product do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 16】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then 10% sodium hydroxide solution is added drop-wise in slurry II under stirring, it is 9 to control terminal pH
Obtain slurry IV, 80 DEG C of ageings take out product filtering after 5 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.
Filter cake after potassium nitrate solution dippings of the 50ml containing potassium 2.3% is dried, 120 DEG C of drying are prepared again, and 500 DEG C of roastings obtain catalyst
C16, takes catalyst sample to do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 17】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, controls terminal pH to obtain slurry IV for 8,
100 DEG C of ageings take out product filtering after 3 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again
Filter cake after potassium nitrate solution dipping drying containing potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C17, take catalyst
Sample does XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 18】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 8 to control terminal pH, obtains slurry IV,
50 DEG C of ageings take out product filtering after 3 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again to contain
Filter cake after the potassium nitrate solution dipping drying of potassium 2.3%, 100 DEG C of drying, 300 DEG C of roastings obtain catalyst C18, take catalyst sample
Product do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 19】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 8 to control terminal pH, obtains slurry IV,
100 DEG C of ageings take out product filtering after 48 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again
Filter cake after potassium nitrate solution dipping drying containing potassium 2.3%, 130 DEG C of drying, 600 DEG C of roastings obtain catalyst C19, take catalyst
Sample does XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 20】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 8 to control terminal pH, obtains slurry IV,
100 DEG C of ageings take out product filtering after 3 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again
Filter cake after potassium nitrate solution dipping drying containing potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C20, take catalyst
Sample does XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 21】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 8 to control terminal pH, obtains slurry IV,
80 DEG C of ageings take out product filtering after 20 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again
Filter cake after potassium nitrate solution dipping drying containing potassium 2.3%, 100 DEG C of drying, 400 DEG C of roastings obtain catalyst C21, take catalyst
Sample does XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 22】
According to【Embodiment 1】Catalyst formulation, simply change preparation process in Con trolling index.I.e.：200ml is prepared to contain
The solution I of the ferric nitrate of iron 5.6% simultaneously stirs, and than surface is 105m by 100g2/ alumina support add solution I stir
It is even, slurry II is obtained, then ammoniacal liquor is added drop-wise in slurry II under stirring, it is 8 to control terminal pH, obtains slurry IV,
80 DEG C of ageings take out product filtering after 2 hours, then washs filter cake with ethanol and deionized water, and 120 DEG C dry.50ml is prepared again to contain
Filter cake after the potassium nitrate solution dipping drying of potassium 2.3%, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C22, take catalyst sample
Product do XRF and BET characterization tests, and test result is shown in Table 1.
【Embodiment 23】
Press【Embodiment 1】Method, simply change the aluminum oxide trade mark.Prepare the solution of the ferric nitrate of 200ml iron content 5.6%
I and stir, than surface be 540m by 100g2/ g alumina supports add solution I and stirred, and obtain slurry II, are then stirring
Mix and ammoniacal liquor is added drop-wise in slurry II under state, it is 8 to control terminal pH, obtains slurry IV, and 80 DEG C of ageings take out product after 5 hours
Filtering, then wash filter cake, 120 DEG C of drying with ethanol and deionized water.Potassium nitrate solution dippings of the 50ml containing potassium 2.3% is prepared again
Filter cake after drying, 120 DEG C of drying, 500 DEG C of roastings obtain catalyst C11, take catalyst sample to do XRF and BET characterization tests, survey
Test result is shown in Table 1.
Table 1
【Embodiment 24】
This example demonstrates that【Embodiment 1~23】Gained catalyst reacts in methyl glycollate oxidation synthesis glyoxylate methyl esters
In application.
Take【Embodiment 1~23】Gained catalyst carries out reaction examination.Using methyl glycollate and air as raw material, reacting
Temperature is 300 DEG C, reaction pressure 0.3MPa, and weight space velocity is 0.8 hour during liquid-1, institute is oxygenous in air and glycolic first
Ester mol ratio is 1：Catalyst is checked and rated under the conditions of 1, reaction result is shown in Table 2.
【Embodiment 25】
This example demonstrates that【Embodiment 1】Gained catalyst is in the reaction of ethyl glycolate oxidation synthesis glyoxylate ethyl ester
Using.
Take【Embodiment 1】Gained catalyst carries out reaction examination.Using ethyl glycolate and air as raw material, in reaction temperature
For 300 DEG C, reaction pressure 0.3MPa, weight space velocity is 0.8 hour during liquid-1, institute is oxygenous in air and an ethyl glycolate rubs
You are than being 1：Reacted under the conditions of 1, reaction result is shown in Table 2.
Table 2
| Embodiment | Catalyst | Conversion ratio, % | Selectivity, % |
| Embodiment 24 | C1 | 97.70 | 95.1 |
| Embodiment 24 | C2 | 97.80 | 89.4 |
| Embodiment 24 | C3 | 96.53 | 94.3 |
| Embodiment 24 | C4 | 97.51 | 95.2 |
| Embodiment 24 | C5 | 96.13 | 95.4 |
| Embodiment 24 | C6 | 97.21 | 93.6 |
| Embodiment 24 | C7 | 95.15 | 94.5 |
| Embodiment 24 | C8 | 97.21 | 93.8 |
| Embodiment 24 | C9 | 95.15 | 92.6 |
| Embodiment 24 | C10 | 95.06 | 89.4 |
| Embodiment 24 | C11 | 95.35 | 85.1 |
| Embodiment 24 | C12 | 96.13 | 92.3 |
| Embodiment 24 | C13 | 97.51 | 92.1 |
| Embodiment 24 | C14 | 97.41 | 95.2 |
| Embodiment 24 | C15 | 96.92 | 94.5 |
| Embodiment 24 | C16 | 96.824 | 94.1 |
| Embodiment 24 | C17 | 97.11 | 94.2 |
| Embodiment 24 | C18 | 95.25 | 93.4 |
| Embodiment 24 | C19 | 95.55 | 95.3 |
| Embodiment 24 | C20 | 97.31 | 94.5 |
| Embodiment 24 | C21 | 97.21 | 94.6 |
| Embodiment 24 | C22 | 96.13 | 94.2 |
| Embodiment 24 | C23 | 95.84 | 93.1 |
| Embodiment 25 | C1 | 97.41 | 95.2 |
【Embodiment 26】
This example demonstrates that【Embodiment 1】Gained catalyst is in the reaction of methyl glycollate oxidation synthesis glyoxylate methyl esters
Change the result of the test of process conditions.
Take the present invention【Embodiment 1】Gained catalyst carries out reaction examination, changes process conditions and is tested, reaction condition
And it the results are shown in Table 3.
Table 3
Claims (10)
1. a kind of method of ethyl glycolate oxidation synthesis glyoxylate ester, including oxygen-containing gas and ethyl glycolate is existed in catalyst
The reactions steps of lower contact generation glyoxylic ester；The catalyst is in terms of parts by weight, including following component：
A) at least one of 0.5~30 part oxide selected from iron or iron active constituent；
B) 0~10 part is selected from least one of IA or Group IIA metal or oxides additive；
C) 70~99 parts of carrier.
2. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that with parts by weight
Meter, the dosage of active constituent is 2~25 parts, and the dosage of auxiliary agent is 0.05~7 part, and the dosage of carrier is 73~97.9 parts.
3. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that the carrier is selected from
At least one of silica, aluminum oxide, zirconium oxide, titanium oxide or Si-Al molecular sieve.
4. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 4, it is characterised in that the carrier is selected from
At least one of aluminum oxide, zirconium oxide or titanium oxide.
5. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that the catalyst ratio
Surface area is 15~700 meters2/ gram.
6. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 5, it is characterised in that the catalyst ratio
Surface area is 50~500 meters2/ gram.
7. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that reaction condition bag
Include：200~450 DEG C, 0~1.5MPa of reaction pressure of reaction temperature, weight space velocity is 0.1~1.5 hour during liquid-1, oxygen-containing gas
It is middle oxygenous with the mol ratio of ethyl glycolate (0.5~2):1.
8. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 7, it is characterised in that reaction condition bag
Include：230~400 DEG C, 0~1.0MPa of reaction pressure of reaction temperature, weight space velocity is 0.2~1.0 hour during liquid-1, oxygen-containing gas
It is middle oxygenous with the mol ratio of ethyl glycolate (0.6~1.5):1.
9. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that add and contain in raw material
The nitrogen of 0.5~10 times of volume of carrier of oxygen is Balance Air.
10. the method for ethyl glycolate oxidation synthesis glyoxylate ester according to claim 1, it is characterised in that the glyoxalic acid
Ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209827A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for synthesizing glyoxylic ester |
| CN112209826A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for preparing aldehyde acetate by glycolate dehydrogenation |
| CN112209818A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for preparing glyoxylic acid ester from glycolic acid ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340748A (en) * | 1979-02-08 | 1982-07-20 | Hoechst Aktiengesellschaft | Process for the manufacture of glyoxylic acid esters |
| US5523459A (en) * | 1994-03-25 | 1996-06-04 | Ube Industries, Ltd. | Preparation of α-keto acid ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209827A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for synthesizing glyoxylic ester |
| CN112209826A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for preparing aldehyde acetate by glycolate dehydrogenation |
| CN112209818A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for preparing glyoxylic acid ester from glycolic acid ester |
| CN112209827B (en) * | 2019-07-12 | 2022-10-11 | 中国石油化工股份有限公司 | Method for synthesizing glyoxylic ester |
| CN112209818B (en) * | 2019-07-12 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing glyoxylic acid ester from glycolic acid ester |
| CN112209826B (en) * | 2019-07-12 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing aldehyde acetate by using glycolate through dehydrogenation |
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| CN107445833B (en) | 2020-08-07 |
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