CN102430421A - Catalyst for synthesizing oxalate and preparation method thereof - Google Patents
Catalyst for synthesizing oxalate and preparation method thereof Download PDFInfo
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- CN102430421A CN102430421A CN2011103367428A CN201110336742A CN102430421A CN 102430421 A CN102430421 A CN 102430421A CN 2011103367428 A CN2011103367428 A CN 2011103367428A CN 201110336742 A CN201110336742 A CN 201110336742A CN 102430421 A CN102430421 A CN 102430421A
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- catalyst
- oxalate
- molybdenum
- hours
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 63
- 238000002803 maceration Methods 0.000 claims description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000002161 passivation Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 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 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229960002510 mandelic acid Drugs 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 229910052594 sapphire Inorganic materials 0.000 abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 150000002826 nitrites Chemical class 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 5
- IKIWQIUJLIJZJB-UHFFFAOYSA-N [N].O=[C] Chemical compound [N].O=[C] IKIWQIUJLIJZJB-UHFFFAOYSA-N 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 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 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- AETNJTRVQSSXDF-UHFFFAOYSA-H [Mo+6].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Mo+6].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AETNJTRVQSSXDF-UHFFFAOYSA-H 0.000 description 1
- PGDDJXSLIWMIRI-UHFFFAOYSA-N acetic acid;molybdenum Chemical compound [Mo].CC(O)=O PGDDJXSLIWMIRI-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229960003116 amyl nitrite Drugs 0.000 description 1
- -1 and wherein Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- ITHNIFCFNUZYLQ-UHFFFAOYSA-N dipropan-2-yl oxalate Chemical compound CC(C)OC(=O)C(=O)OC(C)C ITHNIFCFNUZYLQ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A catalyst for synthesizing oxalate and a preparation method thereof, which uses a carrier alpha-Al2O3The components and contents of the catalyst comprise: 0.01 to 0.5wt% of active component Pd, 0.01 to 1.0wt% of auxiliary agent Mo (beta-Mo)2C in the form of C) and 0.01-1.0 wt% of an auxiliary agent M (Fe, Co, Ni, Cu or Zn) by adopting a step-by-step impregnation method. To carrier alpha-Al2O3Used after being washed, dried and roasted, and is characterized in that the specific surface area is 5-20 m2A pore volume of 0.03-0.13 cm3(ii)/g, the average pore diameter is 10 to 20 nm. The catalyst prepared by the method has certain shape and size, high mechanical strength, low content of noble metal Pd, long service life and good activity and selectivity in the reaction process of synthesizing the glycol by hydrogenating the oxalate. Because Mo and M are adopted to partially replace noble metal Pd, the content and the production cost of the noble metal in the catalyst are reduced, and the catalyst has better economical efficiency.
Description
Technical field
The present invention relates to the synthetic of oxalate, particularly a kind of synthetic Catalysts and its preparation method of oxalate that is used for.
Background technology
Oxalate can be used for making the intermediate of ethylene glycol, oxalic acid, oxamides and some drugs and dyestuff, is important basic chemical industry raw material, and important effect is arranged in C-1 chemistry.The liquid phase synthesis of oxalate is at first proposed in 1966 by U.S.'s combined oil (Unocal) company, adopts PdCl
2-CuCl
2Catalyst, reaction under 125 ℃, 7.0MPa.This method is owing to use chloride catalyst, and equipment corrosion is serious, and for keeping anhydrous state, needs to use a large amount of dehydrating agents, and process economy property is poor.After this, U.S. Arco company and company of Ube Industries Ltd. improve catalyst system, but still fail to solve the equipment corrosion problem.Afterwards; Emerging product company of space portion has developed the technology of synthesis of oxalic ester by gaseous catalysis; JP8242656 special permission communique is at first reported and is adopted the platinum group metal loaded catalyst to carry out the technological process of carbon monoxide and methyl nitrite synthesizing dimethyl oxalate, and reaction pressure 0.5MPa, temperature are 80 ~ 150 ℃.This process mould examination is operation 480h continuously, and the average space-time yield of dimethyl oxalate is 432g/L
Cat/ h.There are many patents to report in succession subsequently again and in catalytic component, add Ti, Mo, Ni, Fe, Ga, Cu, Ce, Zr, Na respectively
2O and SiO
2Catalyst Deng auxiliary agent is formed is applied in the technology of carbon monoxide and nitrites gas-phase dimethyloxalate synthesis, diethy-aceto oxalate and oxalic acid diisopropyl ester.Pd/Al like the CN1381310A report
2O
3Added the Ce auxiliary agent in the catalyst, Pd content is about 0.8 ~ 1.3wt%.The Pd-Ga/Al of CN1055492A report
2O
3Pd content is 0.5 ~ 1.5% in the catalyst.Pd content is generally higher in these catalyst, and Pd is a kind of noble metal, costs an arm and a leg, and high load capacity makes the catalyst cost high, influences its use in industry.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst that is used for synthesis of oxalate and preparation method thereof, shortcomings such as existing catalyst activity is low to overcome, poor stability, precious metals pd load capacity height.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
The synthetic catalyst of oxalate that is used for of the present invention, this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and molybdenum is first auxiliary agent, and metal M is second auxiliary agent, and M is any one among Fe, Co, Ni, Cu or the Zn, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%, molybdenum 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%.
Described α-Al
2O
3The specific area of carrier is 5 ~ 20 m
2/ g, pore volume are 0.03 ~ 0.13 cm
3/ g, average pore size is 10 ~ 20 nm.
The synthetic Preparation of catalysts method of oxalate that is used for of the present invention, catalyst adopts the step impregnation method preparation, may further comprise the steps:
(1) be mixed with maceration extract with molybdenum salt and organic complex by metering, wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1;
(2) with the solution soaking α-Al of step (1)
2O
3Carrier left standstill 3 ~ 20 hours;
(3) after filtration, the drying, carbonization under light hydrocarbon and hydrogen mixed gas atmosphere, light hydrocarbon and hydrogen mol ratio are 1/5 ~ 1/3, wherein light hydrocarbon is CH
4, C
2H
6, C
3H
8, C
2H
4Or C
3H
6In any one; Then at O
2Volume content is 0.2% O
2With promptly get presoma after the passivation under the Ar mixed atmosphere;
(4) salt with palladium, metal M is mixed with maceration extract by metering;
(5) with the presoma in the solution soaking step (3) of step (4), left standstill 2 ~ 12 hours;
(6) filtration, drying add suitable quantity of water, under 40 ~ 90 ℃ of water bath condition, drip precipitating reagent while stirring, and the pH value of regulating mixed system is 6 ~ 13, aging 2 ~ 6 hours;
(7) with 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd) amount of substance 0.5 ~ 2 hour; After filtration, washing, the drying, promptly make catalyst.
Palladium salt in said step (1) and (4), molybdenum salt and metal M salt can be in nitrate, halide, oxalates or the acetate any one, and wherein molybdenum salt can also be ammonium molybdate.
Organic complexing agent in the said step (1) can be in citric acid, lactic acid, mandelic acid or the oxalic acid any one, and wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1.
Precipitating reagent in the said step (6) can be K
2CO
3, Na
2CO
3, KOH, NaOH, NaHCO
3Or KHCO
3Any one.
Reducing agent in the said step (7) can be in hydrazine hydrate, formaldehyde, formic acid, sodium borohydride or the potassium borohydride any one.
Catalyst of the present invention carries out activation processing before using, and activation method is to feed hydrogen-nitrogen mixed gas (H
2Volume content 10% ~ 100%) or carbon monoxide-nitrogen mixed gas (CO volume content 10% ~ 100%) in 150 ~ 450 ℃ of activation processing 2 ~ 4 hours, feed unstripped gas after the catalyst activation treatment and react, unstripped gas carbon monoxide and nitrites are used nitrogen dilution; Unstripped gas contacts with above-mentioned catalyst, and be 0.5 ~ 4 second time of contact, and reaction temperature is 90 ~ 140 ℃, and reaction pressure is normal pressure ~ 1.0MPa.
The synthetic Application of Catalyst condition of oxalate that is used for of the present invention is: adopt fixed bed reactors, catalyst need carry out activation processing before using, and activation method is to feed hydrogen-nitrogen mixed gas (H
2Volume content 10% ~ 100%) or carbon monoxide-nitrogen mixed gas (CO volume content 10% ~ 100%) in 150 ~ 450 ℃ of activation processing 2 ~ 4 hours; Be used for the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalate behind the catalyst activation; Unstripped gas carbon monoxide and nitrites are used nitrogen dilution; The proportion control of carbon monoxide and nitrites is in 15 ~ 30:10 ~ 20 (volume ratio); The described catalyst of unstripped gas and claim 1 time of contact is 0.5 ~ 4 second, and reaction temperature is 90 ~ 140 ℃, and reaction pressure is normal pressure ~ 1.0MPa.
The reaction equation of carbon monoxide and nitrites synthesis of oxalic ester by gaseous catalysis is following:
Wherein: R is an alkyl.
The required nitrites of this reaction can use nitrous acid with the alcohol reaction or by NO, O
2Reaction generates with alcohol, and wherein, alcohol can be selected any saturated fatty alcohol that comprises 1 ~ 8 carbon atom for use, and methyl alcohol, ethanol are the most commonly used.Unstripped gas is used N usually
2As inert gas dilution.
The present invention compared with prior art has following characteristics:
(1) the novel Mo of the inventive method preparation
2C/M/Pd/ α-Al
2O
3Catalyst, the content of noble metal component Pd reduces greatly, has reduced the cost of catalyst.
(2) the present invention is with the α-Al of moulding
2O
3Be carrier, reduced the forming step of catalyst;
(3) catalyst disclosed by the invention has high reaction activity and high and selectivity, and its reactivity worth repeatability is relatively good; Method for preparing catalyst is simple, easy operating, and easy realization of industrial is amplified.
The specific embodiment
The volume of the solution that palladium salt and promoter metal salt are made among the following embodiment is not strict with, and the aqueous solution that is made into can get final product by the submergence carrier.
The present invention reacts the performance of evaluate catalysts with carbon monoxide and methyl nitrite synthesizing dimethyl oxalate, should understand the present invention and can be applicable to carbon monoxide and other nitrites (like nitrous ether (ethyl nitrite), propyl nitrite, butyl nitrite, amyl nitrite etc.) prepared in reaction oxalate.Catalyst places stainless steel reactor; Reactor inside diameter is 15mm, dress thermocouple sheath in the reactor, and loaded catalyst is 3ml; After reduction process finishes; The question response actuator temperature is reduced to reaction and is switched to unstripped gas after temperature required and react, and through beds, by reactor bottom discharged from top to bottom by the product dimethyl oxalate for unstripped gas.
Embodiment 1
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.2wt%Mo+0.1wt%Zn+0.5wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting ammonium molybdate for use, is 1 in maceration extract, to add citric acid by citric acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/5) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select zinc nitrate and palladium for use, be mixed with maceration extract according to the load capacity of Zn and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 4 hours, filters, dries; Add suitable quantity of water, under 50 ℃ of water bath condition, drip NaOH solution while stirring, regulating the pH value is 9.0, aging 2 hours, and add 4 times of hydrazine hydrate solutions then and reduced 1 hour to (Cu+Pd) amount of substance, after filtration, washing, the oven dry, promptly get Mo
2C/Zn/Pd/ α-Al
2O
3Catalyst.
It is carbon monoxide-nitrogen mixed gas of 60% in 240 ℃ of reductase 12s hour that this catalyst uses CO content, cools to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 20%CH
3ONO+30%CO+50%N
2Unstripped gas, be 1 second time of contact, reaction result is listed in the table 1.
Embodiment 2
Take by weighing 10 gram α-Al
2O
3Carrier is by 0.5 wt%Mo+0.01wt%Fe+0.4 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting ammonium molybdate for use, is 0.8 in maceration extract, to add mandelic acid by mandelic acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 12 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select iron chloride and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Fe and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 12 hours; Filter, dry, add suitable quantity of water, under 90 ℃ of water bath condition, drip KOH solution while stirring; The pH value of regulating mixed system is 6.0, wore out 4 hours, with 2 times to the formalin reductase 12 of (Fe+Pd) amount of substance hour; After filtering, wash, drying, promptly get Mo
2C/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 30% in 180 ℃ of reduction 4 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 18%CH
3ONO+30%CO+52%N
2Unstripped gas, be 1 second time of contact, reaction result is listed in the table 1.
Embodiment 3
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 1.0wt%Mo+0.5wt%Co+0.05wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting molybdenum chloride for use, is 2.0 in maceration extract, to add oxalic acid by oxalic acid/molybdenum amount of substance ratio, is 20.0m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 3 hours, takes out in baking oven dry; After the oven dry, at C
3H
8/ H
2(1/4) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cobalt nitrate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Co and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 2 hours, filters, dries; Under 40 ℃ of water bath condition, drip Na while stirring
2CO
3Solution, the pH value of regulating mixed system is 13.0, aging 6 hours, use 20 times of sodium borohydride solutions to reduce then 1.5 hours to (Co+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 60% in 220 ℃ of reduction 3 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+30%CO+55%N
2Unstripped gas, be 2 seconds time of contact, reaction result is listed in the table 1.
Embodiment 4
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.6wt%Mo+0.5wt%Cu+0.3wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting the acetic acid molybdenum for use, is 0.8 in maceration extract, to add mandelic acid by mandelic acid/molybdenum amount of substance ratio, is 15.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 7 hours, takes out in baking oven dry; After the oven dry, at C
2H
4/ H
2(1/3) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cupric oxalate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Cu and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 7 hours, filters, dries; Add suitable quantity of water, under 40 ℃ of water bath condition, drip KHCO while stirring
3Solution, the pH value of regulating mixed system is 9.0, aging 5 hours, use 10 times of formalins to reduce then 1 hour to (Cu+Pd) amount of substance, after filtration, washing, the oven dry, promptly get Mo
2C/Cu/Pd/ α-Al
2O
3Catalyst.
This catalyst use CO content be carbon monoxide-nitrogen mixed gas of 10% in 280 ℃ of reductase 12 .5 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 20%CH
3ONO+20%CO+60%N
2Unstripped gas, be 1.5 seconds time of contact, reaction result is listed in the table 1.
Embodiment 5
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.2wt%Mo+1.0wt%Co+0.5wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting molybdenum trisulfate for use, is 1 in maceration extract, to add citric acid by citric acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cobalt nitrate and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Co and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 4 hours, filters, dries; Add suitable quantity of water, under 50 ℃ of water bath condition, drip NaHCO while stirring
3Solution, the pH value of regulating mixed system is 9.0, aging 2 hours, reduced 1 hour with 3 times of solution of potassium borohydride to (Co+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 10% in 400 ℃ of reduction 5 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+15%CO+70%N
2Unstripped gas, be 0.5 second time of contact, reaction result is listed in the table 1.
Embodiment 6
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 1.0wt%Mo+0.01wt%Fe+0.01 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting ammonium molybdate for use, is 0.5 in maceration extract, to add citric acid by citric acid/molybdenum amount of substance ratio, is 10.0m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 8 hours, takes out in baking oven dry; After the oven dry, at C
2H
6/ H
2(1/4) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select ferric nitrate and palladium for use, be mixed with maceration extract according to the load capacity of Fe and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 12 hours, filters, dries, and adds suitable quantity of water, under 80 ℃ of water bath condition, drips NaHCO while stirring
3Solution, the pH value of regulating mixed system is 11.0, aging 5 hours, reduced 0.5 hour with 15 times of formalins to (Fe+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content is hydrogen-nitrogen mixed gas of 50% in 450 ℃ of reductase 12s hour, cools to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 20%CH
3ONO+30%CO+50%N
2Unstripped gas, be 4 seconds time of contact, reaction result is listed in the table 1.
Embodiment 7
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.8wt%Mo+0.3wt%Ni+0.2wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting the nitric acid molybdenum for use, is 0.4 in maceration extract, to add lactic acid by lactic acid/molybdenum amount of substance ratio, is 20.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 20 hours, takes out in baking oven dry; After the oven dry, at C
3H
6/ H
2(1/5) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select nickel chloride and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Ni and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 10 hours, filters, dries, and adds suitable quantity of water; Under 40 ℃ of water bath condition, drip KOH solution while stirring; The pH value of regulating mixed system is 13.0, wore out 3 hours, with 6 times to the hydrazine hydrate solution reductase 12 of (Ni+Pd) amount of substance .0 hour; After filtering, wash, drying, promptly get Mo
2C/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst use CO content be carbon monoxide-nitrogen mixed gas of 30% in 150 ℃ of reduction 4 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 15%CH
3ONO+20%CO+65%N
2Unstripped gas, be 1.5 seconds time of contact, reaction result is listed in the table 1.
Embodiment 8
Take by weighing 10 gram α-Al
2O
3Carrier is by 0.7 wt%Mo+0.6 wt%Ni+0.1 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: selecting ammonium molybdate for use, is 0.4 in maceration extract, to add citric acid by citric acid/molybdenum amount of substance ratio, is 12.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 16 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, subsequent use after the passivation, be designated as Mo
2C/ α-Al
2O
3Select nickel nitrate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Ni and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 10 hours, filters, dries, and adds suitable quantity of water, under 60 ℃ of water bath condition, drips K while stirring
2CO
3Solution, the pH value of regulating mixed system is 10.0, aging 2 hours, reduced 0.5 hour with 8 times of hydrazine hydrate solutions to (Ni+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst is used pure H
2Gas cools to reaction temperature then in 180 ℃ of reductase 12s hour, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+25%CO+60%N
2Unstripped gas, be 0.72 second time of contact, reaction result is listed in the table 1.
Claims (7)
1. one kind is used for the synthetic catalyst of oxalate, and it is characterized in that: this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and molybdenum is first auxiliary agent, and metal M is second auxiliary agent, and M is any one among Fe, Co, Ni, Cu or the Zn, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%, molybdenum 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%.
2. the synthetic catalyst of oxalate that is used for according to claim 1 is characterized in that: described α-Al
2O
3The specific area of carrier is 5 ~ 20 m
2/ g, pore volume are 0.03 ~ 0.13 cm
3/ g, average pore size is 10 ~ 20 nm.
3. according to each described synthetic Preparation of catalysts method of oxalate that is used among the claim 1-2, it is characterized in that: catalyst adopts the step impregnation method preparation, may further comprise the steps:
(1) be mixed with maceration extract with molybdenum salt and organic complex by metering, wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1;
(2) with the solution soaking α-Al of step (1)
2O
3Carrier left standstill 3 ~ 20 hours;
(3) after filtration, the drying, carbonization under light hydrocarbon and hydrogen mixed gas atmosphere, light hydrocarbon and hydrogen mol ratio are 1/5 ~ 1/3, wherein light hydrocarbon is CH
4, C
2H
6, C
3H
8, C
2H
4Or C
3H
6In any one; Then at O
2Volume content is 0.2% O
2With promptly get presoma after the passivation under the Ar mixed atmosphere;
Salt with palladium, metal M is mixed with maceration extract by metering;
Presoma with in the solution soaking step (3) of step (4) left standstill 2 ~ 12 hours;
Filtration, drying add suitable quantity of water, under 40 ~ 90 ℃ of water bath condition, drip precipitating reagent while stirring, and the pH value of regulating mixed system is 6 ~ 13, aging 2 ~ 6 hours;
With 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd) amount of substance 0.5 ~ 2 hour; After filtration, washing, the drying, promptly make catalyst.
4. the synthetic Preparation of catalysts method of oxalate that is used for according to claim 3; It is characterized in that: the palladium salt in said step (1) and (4), molybdenum salt and metal M salt can be in nitrate, halide, oxalates or the acetate any one, and wherein molybdenum salt can also be ammonium molybdate.
5. the synthetic Preparation of catalysts method of oxalate that is used for according to claim 3; It is characterized in that: the organic complexing agent in the said step (1) can be in citric acid, lactic acid, mandelic acid or the oxalic acid any one, and wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1.
6. the synthetic Preparation of catalysts method of oxalate that is used for according to claim 3, it is characterized in that: the precipitating reagent in the said step (6) can be K
2CO
3, Na
2CO
3, KOH, NaOH, NaHCO
3Or KHCO
3Any one.
7. the synthetic Preparation of catalysts method of oxalate that is used for according to claim 3 is characterized in that: the reducing agent in the said step (7) can be in hydrazine hydrate, formaldehyde, formic acid, sodium borohydride or the potassium borohydride any one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
| CN111085193A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Impregnation method of supported palladium catalyst |
| CN111495388A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof |
| CN111495389A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by carbon monoxide gas-phase coupling ethyl nitrite and preparation method and application thereof |
| CN119588347A (en) * | 2025-02-10 | 2025-03-11 | 东北师范大学 | A hydrogenation catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
-
2011
- 2011-10-31 CN CN 201110336742 patent/CN102430421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
| CN111085193A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Impregnation method of supported palladium catalyst |
| CN111495388A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof |
| CN111495389A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by carbon monoxide gas-phase coupling ethyl nitrite and preparation method and application thereof |
| CN111495389B (en) * | 2020-05-19 | 2022-12-20 | 天津大学 | Catalyst for synthesizing diethyl oxalate through gas-phase coupling of carbon monoxide with ethyl nitrite and its preparation method and application |
| CN111495388B (en) * | 2020-05-19 | 2022-12-20 | 天津大学 | A kind of CO gas-phase coupling ethyl nitrite synthesis diethyl oxalate catalyst and preparation method thereof |
| CN119588347A (en) * | 2025-02-10 | 2025-03-11 | 东北师范大学 | A hydrogenation catalyst and its preparation method and application |
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