CN107445831A - The production method of glyoxylic ester - Google Patents
The production method of glyoxylic ester Download PDFInfo
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- CN107445831A CN107445831A CN201610367956.4A CN201610367956A CN107445831A CN 107445831 A CN107445831 A CN 107445831A CN 201610367956 A CN201610367956 A CN 201610367956A CN 107445831 A CN107445831 A CN 107445831A
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- 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
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The present invention relates to a kind of production method of glyoxylic ester, and it is low mainly to solve the problems, such as that prior art has glyoxylic ester yield.The present invention by using including oxygen-containing gas, ethyl glycolate, diluent and carrier gas contacted in the reactor with catalyst under the conditions of gas phase oxidation the step of；Wherein, the technical scheme that the oxygen-containing gas enters reactor by ceramic distributor 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 production method of glyoxylic 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, under this condition carry out degree shadow of the oxygen concentration height to reaction
Sound is larger, if oxygen skewness, local oxygen concentration is too high easily to make oxidation reaction excessive, influences the receipts of glyoxylic ester
Rate, so it is extremely important to the yield for improving glyoxylic ester to improve oxygen distribution.But all do not have to the report of such reaction at present
There is the problem of considering oxygen distribution, and the yield of glyoxylic ester is not high.
Such as document US4340748 disclose it is a kind of using ethyl glycolate as raw material under the conditions of 100~600 DEG C with oxygenous
Body carries out catalytic gas phase oxidation to it and obtains the method for glyoxylic ester, and the yield of glyoxylic ester is up in liquid product
88.3%, the yield of glyoxylic ester only has 43.5% under the conditions of some.
The content of the invention
The technical problems to be solved by the invention are that prior art has the problem of glyoxylic ester yield is low, there is provided Yi Zhongxin
Production glyoxylic ester method.This method has the characteristics of glyoxylic ester high income.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method for producing glyoxylic ester, bag
Include what oxygen-containing gas, ethyl glycolate, diluent and carrier gas contacted with catalyst in the reactor under the conditions of gas phase oxidation
Step；Wherein, the oxygen-containing gas enters reactor by ceramic distributor.
In above-mentioned technical proposal, the film of the ceramic distributor is Alpha-alumina, silica, titanium oxide or mullite pottery
At least one of porcelain film.
In above-mentioned technical proposal, the membrane aperture of the ceramic distributor is 0.1~5 micron；Preferably 0.1~3 micron.
In above-mentioned technical proposal, the ceramic distributor be configured to reactor radially it is vertical, and height for reaction
The 20~90% of device internal catalyst bed layer height.
In above-mentioned technical proposal, the diluent is selected from least one of water, alcohol, chlorinated hydrocabon or chloracetate.
In above-mentioned technical proposal, the carrier gas is selected from least one of nitrogen, rare gas or rudimentary saturated hydrocarbons.
In above-mentioned technical proposal, the gas phase oxidation condition includes：100~600 DEG C of temperature, pressure 0.001~
10MPa, mass space velocity 0.05~4 hour during ethyl glycolate liquid-1。。
In above-mentioned technical proposal, the mol ratio of the diluent and ethyl glycolate is 0.01:1~10:1, in oxygen-containing gas
Oxygen is 0.1 with ethyl glycolate mol ratio:1~5:1, the mol ratio of carrier gas and ethyl glycolate is 0:1~80:1.
In above-mentioned technical proposal, the catalyst is in terms of parts by weight, including following components：
A) 0.01~20 part of the active component selected from least one of V, Mo, Ag or Cu；
B) at least one of 0.01~20 part Sn, Sb, Bi, K, Na, Li, Mg, Ca or Ba auxiliary agent；
C) 60~99.98 parts of the carrier selected from least one of aluminum oxide, silicate or alumino-silicate.
In above-mentioned technical proposal, the glyoxylic ester is glyoxalic acid methylester or glyoxylic acid ethyl ester.
In above-mentioned technical proposal, the method for preparing catalyst is：
1) by active constituent a) soluble-salt wiring solution-forming I, dried after being impregnated in carrier c), obtain catalyst precarsor；
2) by auxiliary agent b) soluble-salt wiring solution-forming II, the catalyst precarsor that step 1) is waited until is impregnated in, then dry；
3) above-mentioned steps catalyst is calcined, that is, obtains being used for ethyl glycolate oxidation glyoxylic ester catalyst processed.
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 at high temperature
Higher ethyl glycolate conversion ratio can be obtained, over oxidation easily occurs under this condition, produce substantial amounts of carbon dioxide and
Water, so by the present invention in that can be effectively dispersed by oxygen with oxygen distribution ware is done using ceramic membrane, because ceramic
For the pore-size distribution of film at 0.1~5 μm, this, which can just be such that oxygen is formed after by distributor, largely has microscale structure
Oxygen bubble, this more, less bubble smaller than the bubble that the distributor directly formed with pipeline or machining is formed
Size can increase mass transfer area, be advantageous to the uniform mixing of oxygen and ethyl glycolate, local oxygen concentration will not be caused too high, shadow
Ring the selectivity of glyoxylic ester.Preferably ceramic distributor of the present invention highly for catalyst in reactor bed height 20~
90%, this can effectively control the reaction depth at each section of reactor, avoid oxygen from all entering from reactor inlet and lead
Cause porch oxygen concentration high, part material over oxidation, and the reactor second half section then makes methyl glycollate because oxygen concentration is low
The low situation of conversion ratio, the conversion ratio of ethyl glycolate and the yield of glyoxylic ester can be effectively improved, reduce peroxidization.Using
The inventive method, the conversion ratio of ethyl glycolate are more than 97%, and glyoxylic ester yield achieves preferable technology effect more than 90%
Fruit.
Brief description of the drawings
Fig. 1 is the schematic diagram of synthesizing glyoxalic acid ester.
In Fig. 1,1 is oxygen-containing gas pipeline, and 2 be ethyl glycolate and diluent line, and 3 be carrier gas line, and 4 be ceramic membrane point
Cloth device, 5 be reactor, and 6 be reaction product.
Below by embodiment, the invention will be further described.
Embodiment
【Embodiment 1】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.1%, glyoxalic acid methylester yield is 92.7%.
【Embodiment 2】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the silica that membrane aperture is 0.13 μm
Reacted on a catalyst together with methyl glycollate after ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.2%, glyoxalic acid methylester yield is 92.6%.
【Embodiment 3】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the titanium oxide that membrane aperture is 0.24 μm
Reacted on a catalyst together with methyl glycollate after ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.6%, glyoxalic acid methylester yield is 92.5%.
【Embodiment 4】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the mullite that membrane aperture is 0.52 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.3%, glyoxalic acid methylester yield is 92.5%.
【Embodiment 5】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the Alpha-alumina that membrane aperture is 1.5 μm
Reacted on a catalyst together with methyl glycollate after ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.7%, glyoxalic acid methylester yield is 92.3%.
【Embodiment 6】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 2.97 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.5%, glyoxalic acid methylester yield is 91.6%.
【Embodiment 7】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 4.32 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.6%, glyoxalic acid methylester yield is 91.3%.
【Embodiment 8】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 20% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 97.9%, glyoxalic acid methylester yield is 90.1.
【Embodiment 9】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.Use methanol
Methyl glycollate after dilution enters from import 2, carrier gas nitrogen from import 3 enter and the methyl glycollate aqueous solution mixing after together
Into reactor, air enters from import 1, is catalyst bed layer height 40% by height, α-oxygen that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after changing aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
Power 0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is
0.7：1, nitrogen and methyl glycollate mol ratio are 50：1.Product turns through gas-liquid separation sampling analysis, methyl glycollate after reaction
Rate is 98.3%, and glyoxalic acid methylester yield is 90.6%.
【Embodiment 10】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas argon gas enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 90% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, reaction pressure
0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 98.6%, glyoxalic acid methylester yield is 92.5%.
【Embodiment 11】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 600 DEG C, reaction pressure
1MPa, air speed 4h-1, diluent and methyl glycollate mol ratio are 8：1, the mol ratio of oxygen and methyl glycollate is 1：1, nitrogen
It is 50 with methyl glycollate mol ratio：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
99.4%, glyoxalic acid methylester yield is 90.1%.
【Embodiment 12】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 500 DEG C, reaction pressure
2MPa, air speed 3h-1, diluent and methyl glycollate mol ratio are 2：1, the mol ratio of oxygen and methyl glycollate is 0.5：1, nitrogen
Gas and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
99.5%, glyoxalic acid methylester yield is 90.2%.
【Embodiment 13】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 400 DEG C, reaction pressure
3MPa, air speed 2.1h-1, diluent and methyl glycollate mol ratio are 0.8：1, the mol ratio of oxygen and methyl glycollate is 0.7：
1, nitrogen and methyl glycollate mol ratio are 40：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
For 99.1%, glyoxalic acid methylester yield is 91.2%.
【Embodiment 14】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 350 DEG C, reaction pressure
0.3MPa, air speed 1.5h-1, diluent and methyl glycollate mol ratio are 0.2：1, the mol ratio of oxygen and methyl glycollate is
0.7：1, nitrogen and methyl glycollate mol ratio are 50：1.Product turns through gas-liquid separation sampling analysis, methyl glycollate after reaction
Rate is 98.7%, and glyoxalic acid methylester yield is 92.1%.
【Embodiment 15】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 300 DEG C, reaction pressure
0.8MPa, air speed 0.7h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 3：1,
Nitrogen and methyl glycollate mol ratio are 60：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
99.4%, glyoxalic acid methylester yield is 92.3%.
【Embodiment 16】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 100 DEG C, reaction pressure
0.1MPa, air speed 0.051h-1, diluent and methyl glycollate mol ratio are 0.01：1, the mol ratio of oxygen and methyl glycollate
For 1：1, nitrogen and methyl glycollate mol ratio are 10：1.Product turns through gas-liquid separation sampling analysis, methyl glycollate after reaction
Rate is 98.6%, and glyoxalic acid methylester yield is 91.1%.
【Embodiment 17】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, air enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 200 DEG C, reaction pressure
0.1MPa, air speed 0.05h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is
0.1：1, nitrogen and methyl glycollate mol ratio are 40：1.Product turns through gas-liquid separation sampling analysis, methyl glycollate after reaction
Rate is 97%, and glyoxalic acid methylester yield is 90.3%.
【Embodiment 18】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and carrier gas nitrogen enters together to enter with after the mixing of the methyl glycollate aqueous solution from import 3
Enter reactor, oxygen enters from import 1, is catalyst bed layer height 60% by height, the alpha-oxidation that membrane aperture is 0.48 μm
Reacted on a catalyst together with methyl glycollate after aluminium ceramic membrane oxygen distribution device.Controlling reaction temperature is 150 DEG C, reaction pressure
10MPa, air speed 0.1h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate is 5：1,
Nitrogen and methyl glycollate mol ratio are 80：1.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
98.9%, glyoxalic acid methylester yield is 90.2%.
【Embodiment 19】
Catalyst of the 60g containing 3 parts of V, 7 parts of Sn and 90 part of alumina supports is taken to load in reactor as shown in Figure 1.It is dilute with water
Methyl glycollate after releasing enters from import 2, and air enters from import 1, is catalyst bed layer height 60% by height, fenestra
Reacted on a catalyst together with methyl glycollate after the Alpha-alumina ceramic membrane oxygen distribution device that footpath is 0.48 μm.Control reaction temperature
Spend for 250 DEG C, reaction pressure 2MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 10：1, oxygen and glycolic
The mol ratio of methyl esters is 0.7：1, it is not added with carrier gas.Product is through gas-liquid separation sampling analysis, methyl glycollate conversion ratio after reaction
99.4%, glyoxalic acid methylester yield is 90%.
【Embodiment 20】
Catalyst of the 60g containing 0.01 part of V, 5 parts of Sn and 94.99 part of silica supports is taken to load reactor as shown in Figure 1
It is interior.Methyl glycollate after being diluted with water enters from import 2, and carrier gas nitrogen enters from import 3 and the methyl glycollate aqueous solution mixes
Enter reactor after conjunction together, air enters from import 1, by height be catalyst bed layer height 60%, membrane aperture be 0.48 μ
Reacted on a catalyst together with methyl glycollate after m Alpha-alumina ceramic membrane oxygen distribution device.Controlling reaction temperature is 250
DEG C, reaction pressure 0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, oxygen and methyl glycollate
Mol ratio is 0.7：1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, ethanol after reaction
Sour methyl ester conversion rate is 97.1%, and glyoxalic acid methylester yield is 90.1%.
【Embodiment 21】
Catalyst of the 60g containing 20 parts of Ag, 2 parts of Ca and 78 part of 4A type molecular sieve carriers is taken to load in reactor as shown in Figure 1.
Methyl glycollate after being diluted with water enters from import 2, and carrier gas nitrogen is from import 3 into after being mixed with the methyl glycollate aqueous solution
Enter reactor together, air enters from import 1, by height be catalyst bed layer height 60%, membrane aperture be 0.48 μm
Reacted on a catalyst together with methyl glycollate after Alpha-alumina ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, instead
Answer pressure 0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, the mol ratio of oxygen and methyl glycollate
For 0.7：1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, methyl glycollate after reaction
Conversion ratio is 98.7%, and glyoxalic acid methylester yield is 91.2%.
【Embodiment 22】
Catalyst of the 60g containing 10 parts of V, 0.5 part of Bi and 88.5 part of alumina support is taken to load in reactor as shown in Figure 1.
Ethyl glycolate after being diluted with water enters from import 2, and carrier gas nitrogen is from import 3 into after being mixed with the ethyl glycolate aqueous solution
Enter reactor together, air enters from import 1, by height be catalyst bed layer height 60%, membrane aperture be 0.48 μm
Reacted on a catalyst together with ethyl glycolate after Alpha-alumina ceramic membrane oxygen distribution device.Controlling reaction temperature is 250 DEG C, instead
Answer pressure 0.1MPa, air speed 0.5h-1, diluent and ethyl glycolate mol ratio are 1：1, the mol ratio of oxygen and ethyl glycolate
For 0.7：1, nitrogen and ethyl glycolate mol ratio are 50：1.Product is through gas-liquid separation sampling analysis, ethyl glycolate after reaction
Conversion ratio is 98.3%, and glyoxylic acid ethyl ester yield is 92.5%.
【Comparative example 1】
The catalyst of 60g embodiments 1 is taken to load in reactor as shown in Figure 1, and according to【Embodiment 1】Process conditions enter
Row reaction, but without using ceramic membrane oxygen distribution device, but use industrially conventional straight pipe with holes type gas distributor.Use
Methyl glycollate after water dilution enters from import 2, and carrier gas nitrogen enters from import 3 and the mixing of the methyl glycollate aqueous solution is latter
Rise and enter reactor, air enters from import 1, is reacted on a catalyst together with methyl glycollate after gas distributor.
Controlling reaction temperature is 250 DEG C, reaction pressure 0.1MPa, air speed 0.5h-1, diluent and methyl glycollate mol ratio are 1：1, oxygen
The mol ratio of gas and methyl glycollate is 0.7：1, nitrogen and methyl glycollate mol ratio are 50：1.Product is through gas-liquid point after reaction
From sampling analysis, methyl glycollate conversion ratio is 90.1%, and glyoxalic acid methylester yield is 80.4%.
Claims (10)
1. a kind of production method of glyoxylic ester, including oxygen-containing gas, ethyl glycolate, diluent and carrier gas are in gas phase oxidation
Under the conditions of the step of being contacted in the reactor with catalyst；Wherein, the oxygen-containing gas is entered by ceramic distributor and reacted
Device.
2. the production method of glyoxylic ester according to claim 1, it is characterised in that the film of the ceramic distributor be α-
At least one of aluminum oxide, silica, titanium oxide or mullite ceramic film.
3. the production method of glyoxylic ester according to claim 1, it is characterised in that the membrane aperture of the ceramic distributor
For 0.1~5 micron.
4. the production method of glyoxylic ester according to claim 3, it is characterised in that the membrane aperture of the ceramic distributor
For 0.35~3 micron.
5. the production method of glyoxylic ester according to claim 1, it is characterised in that the ceramic distributor is configured to
It is radially vertical with reactor, and the ceramic distributor is highly the 20~90% of catalyst in reactor bed height.
6. the production method of glyoxylic ester according to claim 1, it is characterised in that the diluent is selected from water, alcohol, chlorination
At least one of hydrocarbon or chloracetate；The carrier gas is selected from least one of nitrogen, rare gas or rudimentary saturated hydrocarbons.
7. the production method of glyoxylic ester according to claim 1, it is characterised in that the gas phase oxidation condition bag
Include：100~600 DEG C, 0.001~10MPa of pressure of temperature, mass space velocity 0.05~4 hour during ethyl glycolate liquid-1。
8. the production method of glyoxylic ester according to claim 1, it is characterised in that the mol ratio of diluent and ethyl glycolate
For 0.01:1~10:1, oxygen and ethyl glycolate mol ratio are 0.1 in oxygen-containing gas:1~5:1, carrier gas and ethyl glycolate rub
You are than being 0:1~80:1.
9. according to claim 1 produce glyoxylic ester method, it is characterised in that the catalyst in terms of parts by weight,
Including following components：
A) 0.01~20 part of the active component selected from least one of V, Mo, Ag or Cu；
B) at least one of 0.01~20 part Sn, Sb, Bi, K, Na, Li, Mg, Ca or Ba auxiliary agent；
C) 60~99.98 parts of the carrier selected from least one of aluminum oxide, silicate or alumino-silicate.
10. the production method of glyoxylic ester according to claim 1, it is characterised in that the glyoxylic ester is glyoxalic acid first
Ester or glyoxylic acid ethyl ester.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209829A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glyoxylic ester |
| CN113105328A (en) * | 2021-04-06 | 2021-07-13 | 上海卓笙环保科技有限公司 | Production method for preparing methyl glyoxylate by selective catalysis of methyl glycolate |
| CN114591170A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing glyoxylic acid ester by oxidizing glycolic acid ester |
| CN115672336A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing glyoxylate by oxidation method, preparation method and application thereof |
Citations (1)
| 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 |
-
2016
- 2016-05-30 CN CN201610367956.4A patent/CN107445831B/en active Active
Patent Citations (1)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| CHEN RIZHI ET AL.: "Enhanced phenol hydroxylation with oxygen using a ceramic membrane distributor", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209829A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glyoxylic ester |
| CN112209829B (en) * | 2019-07-12 | 2023-08-08 | 中国石油化工股份有限公司 | Method for producing glyoxylate |
| CN114591170A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing glyoxylic acid ester by oxidizing glycolic acid ester |
| CN114591170B (en) * | 2020-12-07 | 2023-06-06 | 中国科学院大连化学物理研究所 | Method for preparing glyoxylate by oxidizing glycolate |
| CN113105328A (en) * | 2021-04-06 | 2021-07-13 | 上海卓笙环保科技有限公司 | Production method for preparing methyl glyoxylate by selective catalysis of methyl glycolate |
| CN115672336A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing glyoxylate by oxidation method, preparation method and application thereof |
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| CN107445831B (en) | 2020-08-07 |
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