CN107445831B - Process for producing glyoxylic acid esters - Google Patents

Process for producing glyoxylic acid esters Download PDF

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CN107445831B
CN107445831B CN201610367956.4A CN201610367956A CN107445831B CN 107445831 B CN107445831 B CN 107445831B CN 201610367956 A CN201610367956 A CN 201610367956A CN 107445831 B CN107445831 B CN 107445831B
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methyl glycolate
glycolate
oxygen
parts
molar ratio
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CN107445831A (en
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龚海燕
刘国强
宋海峰
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • 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
    • 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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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a production method of glyoxylate, which mainly solves the problem of low yield of glyoxylate in the prior art. The invention adopts a step of contacting oxygen-containing gas, glycolate, diluent and carrier gas with catalyst in a reactor under the condition of gas-phase oxidation reaction; wherein, the technical proposal that the oxygen-containing gas enters the reactor through the ceramic membrane distributor better solves the problem and can be used in the industrial production of preparing the glyoxylic ester by oxidizing the glycolic acid ester.

Description

Process for producing glyoxylic acid esters
Technical Field
The invention relates to a production method of glyoxylic ester.
Background
Glyoxylic acid esters have both aldehyde and ester chemistries and can undergo a variety of reactions, particularly hydrolysis, to produce glyoxylic acid. Glyoxylic acid is an organic intermediate for synthesizing spices, medicines, foods, varnish raw materials, dyes, plastic additives and the like, can be used for producing oral penicillin, vanillin, mandelic acid, allantoin and the like, and therefore the consumption of glyoxylic acid is always increased at home and abroad.
Glyoxylic acid production processes vary from starting material to starting material, currently being as many as a dozen. The most commonly used methods in industry are oxalic acid electrolytic reduction, glyoxal nitric acid oxidation, maleic acid (anhydride) ozonization, and the like. At present, the domestic glyoxylate industry encounters two major problems: firstly, the large-batch and high-quality glyoxylic acid is insufficient in supply, so that the price advantage of downstream products cannot be fully exerted, and the market development of the glyoxylic acid and the downstream products thereof is seriously influenced; secondly, the glyoxalic acid is produced by adopting a glyoxal method basically in China. The fluctuation of the international crude oil price influences the price of the glyoxal and finally influences the price of the glyoxylic acid.
China has abundant coal and natural gas resources, but insufficient petroleum resources, so that a method for opening up a non-petroleum route has important strategic significance in China. In the 70 th 20 th century, under the influence of the world petroleum crisis, a great deal of C1 chemical research mainly based on natural gas and coal-based raw materials is carried out in various countries, and related technologies are rapidly developed in the 90 th century, so that a great breakthrough is made particularly in the aspect of researching the production of ethylene glycol by using coal or natural gas as raw materials, and a great deal of process by-product glycolate is generated, so that the development of a non-petroleum route for preparing the glycolate by oxidizing the glycolate has very high competitiveness.
However, the reaction for synthesizing glyoxylic acid ester by oxidizing glycolate is the first reaction in the whole oxidation reaction process, if the reaction is continued to go downwards, methyl glyoxylate is further oxidized into acid, and then the further oxidation generates a large amount of carbon dioxide and water, and the two reactions can cause the yield of glyoxylic acid ester to be reduced. In addition, the oxidation reaction needs 200-400 ℃ to obtain higher conversion rate of the glycolate, the oxygen concentration under the condition greatly affects the reaction progress, if the oxygen distribution is not uniform, the oxidation reaction is easily excessive due to too high local oxygen concentration, and the yield of the glyoxylate is affected, so that the improvement of the oxygen distribution is very important for improving the yield of the glyoxylate. However, the current reports on the reactions do not consider the problem of oxygen distribution, and the yield of the glyoxylic ester is not high.
For example, US4340748 discloses a process for obtaining glyoxylic esters by vapor phase catalytic oxidation of glycolic acid esters as a starting material with an oxygen-containing gas at 100 to 600 ℃, wherein the yield of glyoxylic esters in the liquid phase product is at most 88.3%, and under some conditions the yield of glyoxylic esters is only 43.5%.
Disclosure of Invention
The invention aims to solve the technical problem of low yield of glyoxylate in the prior art and provides a novel method for producing glyoxylate. The method has the characteristic of high yield of glyoxylic ester.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for producing glyoxylic esters comprising the steps of contacting an oxygen-containing gas, a glycolate, a diluent and a carrier gas with a catalyst in a reactor under gas phase oxidation reaction conditions; wherein the oxygen-containing gas enters the reactor through the ceramic membrane distributor.
In the technical scheme, the membrane of the ceramic membrane distributor is at least one of α -alumina, silicon oxide, titanium oxide or mullite ceramic membrane.
In the technical scheme, the membrane aperture of the ceramic membrane distributor is 0.1-5 microns; preferably 0.1 to 3 μm.
In the technical scheme, the ceramic membrane distributor is arranged to be radially vertical to the reactor, and the height of the ceramic membrane distributor is 20-90% of the height of a catalyst bed layer in the reactor.
In the above technical solution, the diluent is selected from at least one of water, alcohol, chlorinated hydrocarbon or chloroacetate.
In the above technical solution, the carrier gas is at least one selected from nitrogen, a noble gas, and a lower saturated hydrocarbon.
In the above technical solution, the gas phase oxidation reaction conditions include: the temperature is 100-600 ℃, the pressure is 0.001-10 MPa, and the hourly space velocity of the glycolic acid ester liquid is 0.05-4 hours-1。。
In the technical scheme, the molar ratio of the diluent to the glycolate is 0.01: 1-10: 1, the molar ratio of oxygen in the oxygen-containing gas to the glycolate is 0.1: 1-5: 1, and the molar ratio of the carrier gas to the glycolate is 0: 1-80: 1.
In the technical scheme, the catalyst comprises the following components in parts by weight:
a) 0.01-20 parts of at least one active component selected from V, Mo, Ag or Cu;
b) 0.01-20 parts of at least one auxiliary agent of Sn, Sb, Bi, K, Na, L i, Mg, Ca or Ba;
c) 60-99.98 parts of at least one carrier selected from alumina, silicate or aluminosilicate.
In the above technical scheme, the glyoxylate is methyl glyoxylate or ethyl glyoxylate.
In the technical scheme, the preparation method of the catalyst comprises the following steps:
1) preparing soluble salt of the active component a) into a solution I, soaking the solution I in a carrier c), and drying to obtain a catalyst precursor;
2) preparing a soluble salt of the auxiliary agent b) into a solution II, dipping the solution II in the catalyst precursor obtained in the step 1), and drying;
3) roasting the catalyst to obtain the catalyst for preparing the glyoxylate by oxidizing the glycolate.
The reaction for synthesizing glyoxylic ester by oxidizing the glycolic ester is the first-stage reaction in the whole oxidation reaction process, if the reaction continues to go downwards, methyl glyoxylate is further oxidized into acid, and the further oxidation generates a large amount of carbon dioxide and water, and the two reactions can cause the yield of glyoxylic ester to be reduced. And the reaction temperature is higher, so that higher conversion rate of glycolate can be obtained at high temperature generally, and excessive oxidation is easy to occur under the condition to generate a large amount of carbon dioxide and water, so the invention can effectively and uniformly disperse oxygen by using the ceramic membrane as the oxygen distributor, because the pore diameter of the ceramic membrane is distributed at 0.1-5 mu m, a large amount of oxygen bubbles with micro-size structures can be formed after the oxygen passes through the distributor, the oxygen bubbles are much smaller than bubbles formed by directly using a pipeline or a mechanically processed distributor, the small bubble size can increase the mass transfer area, the uniform mixing of the oxygen and glycolate is facilitated, the local oxygen concentration is not too high, and the selectivity of glycolate is not influenced. According to the invention, the height of the ceramic membrane distributor is preferably 20-90% of the height of the catalyst bed layer in the reactor, so that the reaction depth of each section of the reactor can be effectively controlled, the condition that the oxygen concentration at the inlet is high and part of raw materials are excessively oxidized due to the fact that all oxygen enters from the inlet of the reactor, and the conversion rate of methyl glycolate is low due to the low oxygen concentration in the second half section of the reactor is avoided, the conversion rate of glycolate and the yield of glyoxylate can be effectively improved, and the peroxidation reaction is reduced. By adopting the method, the conversion rate of the glycolate is more than 97 percent, the yield of the glyoxylate is more than 90 percent, and better technical effects are obtained.
Drawings
FIG. 1 is a schematic of the synthesis of glyoxylic esters.
In FIG. 1, 1 is an oxygen-containing gas line, 2 is a glycolate and diluent line, 3 is a gas-carrying line, 4 is a ceramic membrane distributor, 5 is a reactor, and 6 is a reaction product.
The invention is further described below by means of specific embodiments.
Detailed Description
[ example 1 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.1% and the yield of methyl glyoxylate was 92.7%.
[ example 2 ]
60g of a catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina support are charged into a reactor as shown in FIG. 1. Methyl glycolate diluted with water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into a reactor, air enters from an inlet 1 and reacts with methyl glycolate on a catalyst after passing through a silica ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.13 mu m. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.2% and the yield of methyl glyoxylate was 92.6%.
[ example 3 ]
60g of a catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina support are charged into a reactor as shown in FIG. 1. Methyl glycolate diluted with water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into a reactor, air enters from an inlet 1 and reacts with methyl glycolate after passing through a titanium oxide ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.24 mu m. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.6% and the yield of methyl glyoxylate was 92.5%.
[ example 4 ]
60g of a catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina support are charged into a reactor as shown in FIG. 1. Methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into a reactor, air enters from an inlet 1 and reacts with methyl glycolate after passing through a mullite aluminum ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.52 mu m. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.3% and the yield of methyl glyoxylate was 92.5%.
[ example 5 ]
60g of a catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and passes through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 1.5 mu m and then is mixed with methyl glycolate, and then the air enters from an outletTogether on a catalyst. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.7% and the yield of methyl glyoxylate was 92.3%.
[ example 6 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 2.97 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.5% and the yield of methyl glyoxylate was 91.6%.
[ example 7 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 4.32 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.6% and the yield of methyl glyoxylate was 91.3%.
[ example 8 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 20 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 97.9% and the yield of methyl glyoxylate was 90.1.
[ example 9 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by methanol enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate through an α -alumina ceramic membrane oxygen distributor with the height of 40 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m on the catalyst, the reaction temperature is controlled to be 250 ℃, the reaction pressure is controlled to be 0.1MPa, and the space velocity is controlled to be 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.3% and the yield of methyl glyoxylate was 90.6%.
[ example 10 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas argon enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and passes through α -The alumina ceramic membrane oxygen distributor is reacted with methyl glycolate on a catalyst. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.6% and the yield of methyl glyoxylate was 92.5%.
[ example 11 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 600 ℃, the reaction pressure is 1MPa, and the space velocity is 4h-1And the molar ratio of the diluent to the methyl glycolate is 8: 1, the molar ratio of oxygen to methyl glycolate is 1:1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 99.4% and the yield of methyl glyoxylate was 90.1%.
[ example 12 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 500 ℃, the reaction pressure is controlled to be 2MPa, and the space velocity is controlled to be 3h-1And the molar ratio of the diluent to the methyl glycolate is 2: 1, the molar ratio of oxygen to methyl glycolate is 0.5: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, the conversion rate of methyl glycolate was 99.5%, and the yield of methyl glyoxylate wasThe rate was 90.2%.
[ example 13 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 400 ℃, the reaction pressure is 3MPa, and the space velocity is 2.1h-1Diluent and methyl glycolate in a 0.8: 1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 40: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 99.1% and the yield of methyl glyoxylate was 91.2%.
[ example 14 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 350 ℃, the reaction pressure is 0.3MPa, and the space velocity is 1.5h-1The molar ratio of the diluent to the methyl glycolate is 0.2: 1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.7% and the yield of methyl glyoxylate was 92.1%.
[ example 15 ]
60g of a catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina support are charged into a reactor as shown in FIG. 1. Methyl glycolate diluted with water is fed from inlet 2, carrier gas nitrogen is fed from inlet 3 and mixed with methyl glycolate aqueous solution, then fed into reactor, and air is fed from inlet 1 and passed through the height of catalystThe bed layer height is 60%, the membrane aperture is 0.48 μm, the α -alumina ceramic membrane oxygen distributor and methyl glycolate react together on the catalyst, the reaction temperature is controlled at 300 ℃, the reaction pressure is 0.8MPa, and the space velocity is 0.7h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 3: 1, the molar ratio of nitrogen to methyl glycolate is 60: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 99.4% and the yield of methyl glyoxylate was 92.3%.
[ example 16 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled at 100 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.051h-1The molar ratio of the diluent to the methyl glycolate is 0.01:1, the molar ratio of oxygen to methyl glycolate is 1:1, the molar ratio of nitrogen to methyl glycolate is 10: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.6% and the yield of methyl glyoxylate was 91.1%.
[ example 17 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, air enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 200 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.05h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.1:1, the molar ratio of nitrogen to methyl glycolate is 40: 1. the product after reaction is separated from gas and liquid, sampled and analyzedThe conversion of methyl glycolate was 97%, and the yield of methyl glyoxylate was 90.3%.
[ example 18 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier gas nitrogen enters from an inlet 3 and is mixed with methyl glycolate aqueous solution and then enters into the reactor, oxygen enters from an inlet 1 and reacts with methyl glycolate on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 150 ℃, the reaction pressure is 10MPa, and the space velocity is 0.1h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 5:1, the molar ratio of nitrogen to methyl glycolate of 80: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.9% and the yield of methyl glyoxylate was 90.2%.
[ example 19 ]
60g of catalyst containing 3 parts of V, 7 parts of Sn and 90 parts of alumina carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, air enters from an inlet 1, and the methyl glycolate react on the catalyst after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is controlled to be 2MPa, and the space velocity is controlled to be 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 10:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, no carrier gas is added. After the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 99.4% and the yield of methyl glyoxylate was 90%.
[ example 20 ]
60g of a catalyst containing 0.01 part of V, 5 parts of Sn and 94.99 parts of silica carrier was charged into a reactor as shown in FIG. 1. methyl glycolate diluted with water was introduced from an inlet 2, carrier gas nitrogen was introduced from an inlet 3 and mixed with a methyl glycolate aqueous solution and introduced into the reactor, air was introduced from an inlet 1 and passed through an α -alumina ceramic membrane having a height of 60% of the height of the catalyst bed and a membrane pore diameter of 0.48 μmThe oxygen distributor is followed by reaction with methyl glycolate over a catalyst. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 97.1% and the yield of methyl glyoxylate was 90.1%.
[ example 21 ]
60g of catalyst containing 20 parts of Ag, 2 parts of Ca and 78 parts of 4A type molecular sieve carrier is loaded into a reactor shown in figure 1, methyl glycolate diluted by water enters from an inlet 2, carrier nitrogen enters from an inlet 3 and enters into the reactor together with a methyl glycolate aqueous solution after being mixed, air enters from an inlet 1 and reacts with methyl glycolate together through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m on the catalyst after passing through the α -alumina ceramic membrane oxygen distributor, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 98.7% and the yield of methyl glyoxylate was 91.2%.
[ example 22 ]
60g of catalyst containing 10 parts of V, 0.5 part of Bi and 88.5 parts of alumina carrier is loaded into a reactor shown in figure 1, ethyl glycolate diluted by water enters from an inlet 2, carrier nitrogen enters from an inlet 3 and enters into the reactor together with an ethyl glycolate aqueous solution after being mixed, air enters from the inlet 1 and reacts with ethyl glycolate together after passing through an α -alumina ceramic membrane oxygen distributor with the height of 60 percent of the height of a catalyst bed layer and the membrane pore diameter of 0.48 mu m, the reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the ethyl glycolate is 1:1, the molar ratio of oxygen to ethyl glycolate is 0.7: 1, the molar ratio of nitrogen to ethyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, the conversion rate of ethyl glycolate was 98.3%, and the ethyl glyoxylateThe yield thereof was found to be 92.5%.
[ COMPARATIVE EXAMPLE 1 ]
60g of the catalyst of example 1 was charged in a reactor as shown in FIG. 1, and the reaction was carried out under the process conditions as described in [ example 1 ], but instead of using a ceramic membrane oxygen distributor, a porous straight tube type gas distributor which is commonly used in the industry was used. That is, methyl glycolate diluted with water is fed from an inlet 2, carrier gas nitrogen is fed from an inlet 3 and mixed with methyl glycolate aqueous solution and fed into a reactor, and air is fed from an inlet 1 and reacted with methyl glycolate on a catalyst after passing through a gas distributor. The reaction temperature is controlled to be 250 ℃, the reaction pressure is 0.1MPa, and the space velocity is 0.5h-1And the molar ratio of the diluent to the methyl glycolate is 1:1, the molar ratio of oxygen to methyl glycolate is 0.7: 1, the molar ratio of nitrogen to methyl glycolate is 50: 1. after the reaction, the product was analyzed by gas-liquid separation and sampling, and the conversion rate of methyl glycolate was 90.1% and the yield of methyl glyoxylate was 80.4%.

Claims (6)

1. A process for producing glyoxylic esters comprising the steps of contacting an oxygen-containing gas, a glycolate, a diluent and a carrier gas with a catalyst in a reactor under gas phase oxidation reaction conditions; wherein the oxygen-containing gas enters the reactor through the ceramic membrane distributor; the membrane aperture of the ceramic membrane distributor is 0.1-5 microns;
the ceramic membrane distributor is arranged to be radially vertical to the reactor, and the height of the ceramic membrane distributor is 20-90% of the height of a catalyst bed layer in the reactor;
the gas phase oxidation reaction conditions include: the temperature is 100-600 ℃, the pressure is 0.001-10 MPa, and the hourly space velocity of the glycolic acid ester liquid is 0.05-4 hours-1；
The molar ratio of the diluent to the glycolate is 0.01: 1-10: 1, the molar ratio of oxygen in the oxygen-containing gas to the glycolate is 0.1: 1-5: 1, and the molar ratio of the carrier gas to the glycolate is 0: 1-80: 1.
2. The method of claim 1, wherein the membrane of the ceramic membrane distributor is at least one of α -alumina, silica, titania, or mullite ceramic membrane.
3. The method for producing glyoxylic acid esters according to claim 1, wherein the ceramic membrane distributor has a membrane pore size of 0.35 to 3 μm.
4. The method for producing glyoxylic esters according to claim 1, characterized in that the diluent is selected from at least one of water, alcohols, chlorinated hydrocarbons or chloroacetates; the carrier gas is selected from at least one of nitrogen, noble gases or lower saturated hydrocarbons.
5. The method for producing glyoxylic esters according to claim 1, characterized in that the catalyst comprises the following components in parts by weight:
a) 0.01-20 parts of at least one active component selected from V, Mo, Ag or Cu;
b) 0.01-20 parts of at least one auxiliary agent of Sn, Sb, Bi, K, Na, L i, Mg, Ca or Ba;
c) 60-99.98 parts of at least one carrier selected from alumina, silicate or aluminosilicate.
6. The method for producing glyoxylic acid esters according to claim 1, wherein the glyoxylic acid ester is methyl glyoxylate or ethyl glyoxylate.
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CN112209829B (en) * 2019-07-12 2023-08-08 中国石油化工股份有限公司 Method for producing glyoxylate
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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
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US4340748A (en) * 1979-02-08 1982-07-20 Hoechst Aktiengesellschaft Process for the manufacture of glyoxylic acid esters

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