CN112209832A - Method for synthesizing glycolate from oxalate - Google Patents

Method for synthesizing glycolate from oxalate Download PDF

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Publication number
CN112209832A
CN112209832A CN201910634942.8A CN201910634942A CN112209832A CN 112209832 A CN112209832 A CN 112209832A CN 201910634942 A CN201910634942 A CN 201910634942A CN 112209832 A CN112209832 A CN 112209832A
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catalyst
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slurry
oxalate
solution
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CN112209832B (en
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龚海燕
刘俊涛
孙凤侠
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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
    • C07C67/31—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 functional groups containing oxygen only in singly bound form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for synthesizing glycolate by oxalate, which comprises the step of contacting oxalate with mixed gas containing hydrogen and carbon monoxide in the presence of a catalyst to react to generate glycolate. In the invention, carbon monoxide is added while hydrogen is introduced in the reaction of synthesizing the glycolate, so that the selectivity of the methyl glycolate is improved.

Description

Method for synthesizing glycolate from oxalate
Technical Field
The invention relates to a method for synthesizing glycolate by oxalate.
Background
Glycolic acid ester has a hydroxyl group structure and an ester group structure, has chemical properties of alcohol and ester, can perform hydrolysis reaction, carbonylation reaction, oxidation reaction and the like, and is an important chemical raw material. Can be widely used in many fields such as fuel, pesticide, medicine, spice, feed, chemical engineering and the like.
Due to the wide application of glycolate, the glycolate is also researched very much at home and abroad. The main production route at present abroad is a carbonylation route which adopts formaldehyde as a raw material, under the action of concentrated sulfuric acid or boron trifluoride and other catalysts, formaldehyde aqueous solution and CO are firstly condensed to generate glycolic acid at the high temperature of about 70.9MPa, and then the glycolic acid is esterified by methanol to obtain the methyl glycolate. The method has the disadvantages that the strong acid catalyst seriously corrodes reaction equipment, and has high requirements on the equipment due to high-pressure reaction, and the equipment has large one-time investment and cannot be produced in a large scale. The production of the methyl glycolate in China mainly adopts a chloroacetic acid method and a formaldehyde and hydrocyanic acid addition method, wherein the chloroacetic acid method is a process route for mixing, reacting and re-esterifying chloroacetic acid and caustic soda solution, the production of the chloroacetic acid adopts acetic acid as a raw material and sulfur as a catalyst, and the production of the chloroacetic acid adopts a chlorine method. The method for preparing methyl glycolate by using formaldehyde and hydrocyanic acid as raw materials is characterized by that it uses formaldehyde and hydrocyanic acid as raw materials, and makes them produce hydroxy acetonitrile under the condition of sulfuric acid catalysis, then makes them undergo the processes of hydrolysis and esterification so as to obtain the invented methyl glycolate whose total yield is 80%.
In the 70 th 20 th century, under the influence of the world petroleum crisis, a great deal of C1 chemical research mainly using natural gas and coal-based raw materials is carried out in various countries, the related technologies are rapidly developed in the 90 th century, and a major breakthrough is made particularly in the aspect of researching the production of ethylene glycol by using coal or natural gas as raw materials, the process route of synthesizing oxalate by gas phase catalysis of CO and methyl nitrite is mature, and a plurality of pilot-scale tests and industrialized devices are built at present. Therefore, the development of a method for preparing methyl glycolate by hydrogenation by using oxalate as a raw material is significant. In the methods for preparing glycolate by hydrogenating oxalate reported in related literatures and patents at present, oxalate and pure hydrogen are reacted, and the yield of glycolate is generally low.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synthesizing glycolate by oxalate.
According to the invention, the method for synthesizing the glycolate by the oxalate comprises the step of contacting and reacting the oxalate with a mixed gas containing hydrogen and carbon monoxide in the presence of a catalyst to generate the glycolate.
According to a preferred embodiment of the present invention, the ratio of the volume of carbon monoxide to the sum of the volumes of hydrogen and carbon monoxide in the mixed gas is 0.01 to 10%, and may be, for example, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and any value therebetween, and is preferably 0.03 to 5%.
According to a preferred embodiment of the invention, the mixed gas consists of hydrogen and carbon monoxide.
According to a preferred embodiment of the invention, the mass space velocity of the oxalate in the reaction process is 0.05-6h-1For example, it may be 0.05h-1、0.1h-1、0.2h-1、0.5h-1、1.0h-1、2.0h-1、3.0h-1、4.0h-1、5.0h-1、6.0h-1And any value in between, preferably 0.1-5h-1More preferably 0.2 to 3 hours-1。
According to a preferred embodiment of the present invention, in the above reaction process, the molar ratio of hydrogen to oxalate is 10 to 150, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 and any value therebetween, preferably 20 to 130, and more preferably 25 to 120.
According to a preferred embodiment of the present invention, in the above reaction process, the temperature of the contact reaction is 120-.
According to a preferred embodiment of the present invention, in the above reaction process, the pressure of the contact reaction is 1 to 5MPa, and may be, for example, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 5MPa or any value therebetween, preferably 1.2 to 4MPa, more preferably 1.5 to 3.5 MPa.
According to a preferred embodiment of the present invention, the catalyst comprises the following components in parts by weight:
a)1-20 parts of an active component, the active component being silver and optionally palladium;
b)0-10 parts of an auxiliary agent; the auxiliary agent is selected from one or more of barium, zinc, calcium, magnesium, zirconium, cobalt, manganese, cerium, iron, lanthanum and molybdenum;
c)70-99 parts of a carrier; the carrier is one or more selected from the group consisting of alumina, silica, SBA-16, ZSM, MCM-22 and MCM-36 molecular sieves.
According to a preferred embodiment of the present invention, the active component in the catalyst may be 1 part, 2 parts, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts and any value therebetween, preferably 2 to 15 parts, in parts by weight; the auxiliary agent can be 0 part, 0.01 part, 0.1 part, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts and any value between the parts, and preferably 0.1-7 parts; the carrier may be 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 99 parts and any value therebetween, and is preferably 78 to 97.9 parts.
According to a preferred embodiment of the invention, the active component contains both silver and palladium, preferably in a mass ratio of silver to palladium of 2 to 50:1, for example 2: 1, 6: 1, 10: 1, 12: 1, 16: 1, 20: 1, 22: 1, 26: 1, 30: 1, 32: 1, 36: 1, 40: 1, 42: 1, 46: 1, 50:1 and any value in between, preferably 10 to 20: 1.
According to a preferred embodiment of the invention, the specific surface area of the catalyst is 150-800m2A ratio of/g, for example 150m2/g、200m2/g、250m2/g、300m2/g、350m2/g、400m2/g、450m2/g、500m2/g、550m2/g、600m2/g、650m2/g、700m2/g、750m2/g、800m2G and any value in between, preferably 250-600m2/g。
According to a preferred embodiment of the invention, the catalyst has an average pore size of 6 to 20nm, for example 6nm, 6.5nm, 7nm, 7.5nm, 8nm, 8.5nm, 9nm, 9.5nm, 10nm, 10.5nm, 11nm, 11.5nm, 12nm, 12.5nm, 13nm, 13.5nm, 14nm, 14.5nm, 15nm, 15.5nm, 16nm, 16.5nm, 17nm, 17.5nm, 18nm, 18.5nm, 19nm, 19.5nm, 20nm and any value in between, preferably 7.5 to 15 nm.
According to a preferred embodiment of the invention, the catalyst has a pore volume of 0.6 to 1.5cm3Per g, for example, may be 0.6cm3/g、0.7cm3/g、0.8cm3/g、0.9cm3/g、1.0cm3/g、1.1cm3/g、1.2cm3/g、1.3cm3/g、1.4cm3/g、1.5cm3G and any value therebetween, preferably 0.7-1.3cm3/g。
According to a preferred embodiment of the invention, the hydrogen sorption amount of the catalyst is 40-200. mu. mol/g, for example 40, 60, 80, 100, 120, 140, 160, 180, 200. mu. mol/g and any value in between, preferably 60-160. mu. mol/g.
According to a preferred embodiment of the present invention, the preparation method of the catalyst comprises the steps of:
step S1, dissolving soluble salt of the active component and soluble salt of the auxiliary agent in a solvent to form a solution I;
step S2, uniformly mixing the carrier powder and adding the carrier powder into the solution I to obtain slurry II;
step S3, preparing at least one of carbonate, bicarbonate, hydroxide of alkali metal or inorganic ammonia water into solution III;
step S4, adding the solution III into the slurry II, controlling the pH value of the reaction end point to be 6-8.5, and aging at 60-140 ℃ for 0.5-48 hours to obtain slurry IV;
and step S5, drying a filter cake obtained after filtering and washing the slurry IV at 80-120 ℃, roasting at 300-550 ℃, and tabletting to obtain the catalyst.
According to a preferred embodiment of the invention, in solution I, the concentration of the soluble salt of the active ingredient is between 0.0001 and 0.5mol/L, and may be, for example, 0.0001mol/L, 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L and any value therebetween, preferably between 0.002 and 0.15 mol/L.
According to a preferred embodiment of the invention, in the solution I, the concentration of the soluble salt of the auxiliary agent is 0 to 0.5mol/L, for example, 0.0001mol/L, 0.001mol/L, 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L and any value therebetween, preferably 0.01 to 0.08 mol/L.
According to a preferred embodiment of the invention, the catalyst is subjected to a reduction treatment before use. Preferably, the reduction treatment mode is as follows: and (3) carrying out reduction by temperature programming in a reducing atmosphere, wherein the reducing atmosphere is hydrogen or a mixed gas of hydrogen and carbon monoxide.
According to the preferred embodiment of the present invention, the volume space velocity of the reducing atmosphere during the reduction treatment is 100-3000h-1The preferable range is 300-2000h-1(ii) a The temperature is programmed to 100-330 ℃, and the preferred range is 150-230 ℃; the reduction time is 2 to 40 hours, preferably 8 to 30 hours.
The oxalate hydrogenation reaction is a series reaction, the target product glycolate is an intermediate product in the series reaction, and if the target product glycolate is further reacted, ethylene glycol and ethanol are generated, so that the conversion of the oxalate is improved in the reaction process, and the reaction step is controlled to be the step of hydrogenating the oxalate to the glycolate as far as possible, so that the yield of the target product is improved. The invention selects silver and optional palladium to prepare the bimetallic active component catalyst, the catalyst can not only obtain weak absorption hydrogen, but also improve the absorption of hydrogen on the catalyst due to bimetallic coordination, and improve the conversion rate of the catalyst to dimethyl oxalate. Meanwhile, part of carbon monoxide is added into the reaction system for competitive adsorption with hydrogen, CO is adsorbed on a strong activity center, and the reaction process is controlled, so that the yield of methyl glycolate is improved.
By using the technical scheme of the invention, the highest conversion rate of the oxalate can reach 99.96%, the yield of the glycolate can reach 93.09%, and a better technical effect is achieved.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In the examples of the invention, the test and characterization methods used were as follows:
the specific surface area, pore volume and average pore diameter of the catalyst were measured on a multi-channel physisorption instrument model 3000 of Micromeritics TriStar, mike instruments, usa.
The hydrogen adsorption amount of the catalyst is measured by adopting a chemical adsorption instrument, and the test steps are as follows: weighing a certain amount of catalyst, placing the catalyst in a sample cell, reducing the catalyst at 300 ℃ by using hydrogen, then blowing the catalyst by using nitrogen at 500 ℃, naturally cooling the catalyst to room temperature, and using 10% H with the flow rate of 30mL/min2Adsorbing the mixed gas of 90% Ar for 30min, then purging with pure argon until the baseline is stable, raising the temperature to 600 ℃ at 10 ℃/min, and simultaneously detecting the desorbed hydrogen by a TCD detector.
Example 1
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of which the concentration is one gram to the solution I to obtain a slurry II, adding 3mol/L ammonium bicarbonate water as a precipitator to the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, and drying at 400 DEG CRoasting for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthesized glycolate catalyst CA 1.
Example 2
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.04mol/L of silver nitrate, 0.002mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 84.5g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 2.
Example 3
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.14mol/L of silver nitrate, 0.0068mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 74g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 3.
Example 4
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.017mol/L of silver nitrate, 0.001mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 87g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 4.
Example 5
Adding certain amounts of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.009mol/L of silver nitrate, 0.0004mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 88g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 5.
Example 6
Adding certain amounts of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.177mol/L of silver nitrate, 0.009mol/L of palladium nitrate and 0.01mol/L of ammonium molybdate, and stirring to obtain 69g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 6.
Example 7
Will be fixedAdding silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L silver nitrate and 0.0036mol/L palladium nitrate, and stirring to obtain 82g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 7.
Example 8
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.001mol/L of ammonium molybdate, and stirring to obtain 82g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 8.
Example 9
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.07mol/L of ammonium molybdate, and stirring to obtain 75g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of which the concentration is one gram to the solution I to obtain slurry II, adding ammonium bicarbonate water of which the concentration is 3mol/L to the slurry II as a precipitator, and controlling the pH value of the end pointAnd 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthesized glycolate catalyst CA 9.
Example 10
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.1mol/L of ammonium molybdate, and stirring to obtain 72.5g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 10.
Example 11
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.007mol/L of cerium nitrate, and stirring to obtain 81g of solution I with the specific surface of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 11.
Example 12
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate and 0.017mol/L of cobalt nitrate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 12.
Example 13
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 13.
Example 14
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 91g of solution I with the specific surface area of 398.61m2G, average pore diameter of 12.19nm and pore volume of 0.93cm3Adding alumina per gram into the solution I to obtain a slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end-point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 14.
Example 15
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 91g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3Adding silicon dioxide per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end-point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 15.
Example 16
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 76g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3Silica/g, silicon to aluminium ratio of 5g 316, specific surface 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3ZSM-5 in g and a specific surface of 398.61m of 10g2G, average pore diameter of 12.19nm and pore volume of 0.93cm3Adding alumina per gram into the solution I to obtain a slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end-point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 16.
Example 17
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3The specific surface area of silica/g and pure silicon 10g was 575.44m2G, average pore diameter of 6.96nm and pore volume of 0.81cm3Adding SBA-16 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging for 6 hours at 100 ℃, filtering and washing the slurry to obtain a filter cake, drying for 10 hours at 120 ℃, roasting for 5 hours at 400 ℃, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 17.
Example 18
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3Silica/g and 10g of silica to alumina ratio 152, specific surface 214.0m2G, average pore diameter of 2.38nm and pore volume of 0.48cm3Adding ZSM-35 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging for 6 hours at 100 ℃, filtering and washing the slurry to obtain a filter cake, drying for 10 hours at 120 ℃, roasting for 5 hours at 400 ℃, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 18.
Example 19
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 91g of pure silicon with the specific surface area of 575.44m2G, average pore diameter of 6.96nm and pore volume of 0.81cm3Adding SBA-16 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging for 6 hours at 100 ℃, filtering and washing the slurry to obtain a filter cake, drying for 10 hours at 120 ℃, roasting for 5 hours at 400 ℃, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 19.
Example 20
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution containing 0.073mol/L of silver nitrate, 0.0015mol/L of palladium nitrate,0.0021mol/L cerium nitrate and 0.0073mol/L ammonium molybdate solution I, 81g specific surface area 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 20.
Example 21
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.05mol/L of silver nitrate, 0.0026mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 21.
Example 22
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.067mol/L of silver nitrate, 0.007mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of which the concentration is one gram to the solution I to obtain slurry II, adding ammonium bicarbonate water of which the concentration is 3mol/L to the slurry II as a precipitator, controlling the end point pH to be 6.5, and aging for 6 hours at 100 DEG CThen, the slurry is filtered and washed, the obtained filter cake is dried for 10 hours at 120 ℃, roasted for 5 hours at 400 ℃, and pressed and formed after roasting, so that the oxalate synthesized glycolate catalyst CA22 is obtained.
Example 23
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.002lmol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 175.38m2G, average pore diameter of 16.88nm and pore volume of 0.64cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 23.
Example 24
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 801.67m2G, average pore diameter of 6.54nm and pore volume of 1.27cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 24.
Example 25
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare the silver nitrate, palladium nitrate and cerium nitrate, wherein the amount of the silver nitrate, the palladium nitrate and the ammonium molybdate is 0.07mol/L, the amount of the palladium nitrate is 0.0036mol/L, the amount of the cerium nitrate is 0.0021mol/L and the amount of the cerium nitrate0.0073mol/L of ammonium molybdate solution I, 81g of which had a specific surface area of 240.15m2G, average pore diameter of 13.15nm and pore volume of 0.74cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 25.
Example 26
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 498.12m2G, average pore diameter of 7.24nm and pore volume of 1.03cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 100 ℃ for 6 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 26.
Example 27
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 65 ℃ for 0.5 hour, and then passing the slurry throughFiltering and washing, drying the obtained filter cake for 10 hours at 120 ℃, roasting for 5 hours at 400 ℃, and tabletting and forming after roasting to obtain the oxalate synthesized glycolate catalyst CA 27.
Example 28
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring the solution I until 81g of solution I has a specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging at 140 ℃ for 48 hours, filtering and washing the slurry to obtain a filter cake, drying at 120 ℃ for 10 hours, roasting at 400 ℃ for 5 hours, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 28.
Example 29
Adding a certain amount of silver nitrate, palladium nitrate and ammonium molybdate into 1 liter of deionized water to prepare a solution I containing 0.07mol/L of silver nitrate, 0.0036mol/L of palladium nitrate, 0.0021mol/L of cerium nitrate and 0.0073mol/L of ammonium molybdate, and stirring to obtain 81g of solution I with the specific surface area of 448.33m2G, average pore diameter of 12.51nm and pore volume of 1.09cm3A silica/g to 10g silicon to aluminium ratio of 316, a specific surface of 220.4m2G, average pore diameter of 3.44nm and pore volume of 0.45cm3Adding ZSM-5 of per gram into the solution I to obtain slurry II, adding 3mol/L ammonium bicarbonate water serving as a precipitator into the slurry II, controlling the end point pH to be 6.5, aging for 6 hours at 100 ℃, filtering and washing the slurry to obtain a filter cake, drying for 10 hours at 120 ℃, roasting for 5 hours at 550 ℃, and tabletting and forming after roasting to obtain the oxalate synthetic glycolate catalyst CA 29.
Application example 1
The catalysts obtained in examples 1 to 29 were charged into a fixed bed reactor and reduced by hydrogen at a temperature programmed. Wherein the volume space velocity of the hydrogen is 1000m3·h-1/m3The temperature is programmed to 180 DEG CThe temperature was maintained for 20 hours, and after the completion of the reduction, the reactor temperature was adjusted to the reaction temperature.
Dimethyl oxalate is taken as a raw material, is mixed with hydrogen containing 1 percent (volume content) of carbon monoxide in advance, and then the mixture is reacted at the temperature of 210 ℃, the reaction pressure of 2.5MPa and the weight space velocity of the dimethyl oxalate of lg/g-1And the catalyst is contacted and reacted under the condition that the molar ratio of hydrogen to oxalate is 80 to generate an effluent containing methyl glycolate, and the product is analyzed by gas chromatography, and the result is shown in a table 1 a.
Application example 2
The catalyst obtained in example 1 was reduced and evaluated in the same manner as in application example 1 except that the raw material was changed to diethyl oxalate, and the results are shown in Table 1 b.
Application example 3
The catalyst obtained in example 1 was reduced by heating under the conditions shown in Table 2, and after completion of the reduction, the reactor temperature was adjusted to the reaction temperature. The contact reaction of dimethyl oxalate with the catalyst was carried out under the conditions shown in Table 2 to produce an effluent containing methyl glycolate, and the product was analyzed by gas chromatography, the results of which are shown in Table 2.
Comparative example 1
The catalyst prepared in example 1 was used, and the reduction conditions of application example 1 were followed, i.e., the catalyst was charged into a fixed bed reactor and reduced by hydrogen at a temperature programmed. Wherein the volume space velocity of the hydrogen is 1000h-1And (3) raising the temperature to 180 ℃ by a program, keeping the temperature for 20 hours, and adjusting the temperature of the reactor to the reaction temperature after the reduction is finished.
Dimethyl oxalate is taken as a raw material, mixed with pure hydrogen in advance, and then subjected to reaction at the temperature of 210 ℃, the reaction pressure of 2.5MPa and the weight space velocity of the oxalate of 1g/g.h-1And the product is subjected to gas chromatographic analysis, the conversion rate of the oxalate is 98.47 percent and the selectivity of the methyl glycolate is 81.33 percent.
Comparative example 2
Reduction of application example 1 Using the catalyst prepared in example 1The condition is that the catalyst is loaded into a fixed bed reactor and reduced by hydrogen programmed temperature rise. Wherein the volume space velocity of the hydrogen is 1000h-1And (3) raising the temperature to 180 ℃ by a program, keeping the temperature for 20 hours, and adjusting the temperature of the reactor to the reaction temperature after the reduction is finished.
Dimethyl oxalate is taken as a raw material, is mixed with hydrogen containing 15 percent of carbon monoxide in advance, and then the mixture is reacted at the temperature of 210 ℃, the reaction pressure of 2.5MPa and the weight space velocity of the oxalate of 1g/g.h-1And the product is subjected to gas chromatographic analysis, the conversion rate of the oxalate is 89.47 percent and the selectivity of the methyl glycolate is 83.2 percent.
Comparative example 3
Using the catalyst prepared in example 1, the catalyst was charged into a fixed bed reactor and reduced by hydrogen at a temperature programmed. Wherein the volume space velocity of the hydrogen is 1000h-1And (3) raising the temperature to 180 ℃ by a program, keeping the temperature for 20 hours, and adjusting the temperature of the reactor to the reaction temperature after the reduction is finished.
Dimethyl oxalate is taken as a raw material, mixed with hydrogen containing 1 percent (volume) of nitrogen in advance, and then the mixture is reacted at the temperature of 210 ℃, the reaction pressure of 2.5MPa and the weight space velocity of the oxalate of 1g/g.h-1And the product is subjected to gas chromatographic analysis, the conversion rate of the oxalate is 87.33 percent and the selectivity of the methyl glycolate is 81.56 percent.
TABLE 1a
Figure BDA0002128819320000161
Figure BDA0002128819320000171
Figure BDA0002128819320000181
In Table 1a, the parts are parts by mass
TABLE 1b
Figure BDA0002128819320000182
In Table 1b, the parts are parts by mass
TABLE 2
Figure BDA0002128819320000183
Figure BDA0002128819320000191
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A method for synthesizing glycolate by oxalate comprises the step of contacting oxalate with a mixed gas containing hydrogen and carbon monoxide in the presence of a catalyst to react to generate glycolate.
2. A method according to claim 1, characterized in that the ratio of the volume of carbon monoxide to the sum of the volumes of hydrogen and carbon monoxide in the mixed gas is 0.01-10%, preferably 0.03-5%.
3. The method according to claim 1 or 2, wherein the mixed gas consists of hydrogen and carbon monoxide.
4. A process according to any one of claims 1 to 3, wherein the mass space velocity of the oxalate ester is 0.05-6h-1Preferably 0.1 to 5h-1More preferably 0.2 to 3 hours-1(ii) a And/or the presence of a gas in the gas,
the molar ratio of hydrogen to oxalate is 10-150, preferably 20-130, more preferably 25-120; and/or the presence of a gas in the gas,
the temperature of the contact reaction is 120-260 ℃, preferably 130-250 ℃, and more preferably 160-230 ℃; and/or the presence of a gas in the gas,
the pressure of the contact reaction is 1 to 5MPa, preferably 1.2 to 4MPa, more preferably 1.5 to 3.5 MPa.
5. The process according to any one of claims 1 to 4, characterized in that the catalyst comprises the following components in parts by weight:
a)1-20 parts, preferably 2-15 parts of active components, the active components being silver and optionally palladium;
b)0-10 parts of assistant, preferably 0.1-7 parts of assistant, wherein the assistant is selected from one or more of barium, zinc, calcium, magnesium, zirconium, cobalt, manganese, cerium, iron, lanthanum and molybdenum;
c)70-99 parts, preferably 78-97.9 parts of carrier; the carrier is one or more selected from the group consisting of alumina, silica, SBA-16, ZSM, MCM-22 and MCM-36 molecular sieves.
6. The method according to claim 5, wherein the active components are silver and palladium, preferably the mass ratio of silver to palladium is 2-50: 1.
7. The method as claimed in any one of claims 1 to 6, wherein the specific surface area of the catalyst is 150-800m2In terms of/g, preference is given to250-600m2/g。
8. A process according to any one of claims 1 to 7, characterised in that the catalyst has an average pore diameter of 6 to 20nm, preferably 7.5 to 15 nm.
9. The process according to any one of claims 1 to 8, wherein the catalyst has a pore volume of from 0.6 to 1.5cm3In g, preferably from 0.7 to 1.3cm3/g。
10. A process according to any one of claims 1 to 9, characterised in that the hydrogen sorption amount of the catalyst is 40 to 200 μmol/g, preferably 60 to 160 μmol/g.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824997A (en) * 1988-01-25 1989-04-25 Monsanto Company Method for preparation of alkyl glycolates
JP2004331531A (en) * 2003-05-02 2004-11-25 Ube Ind Ltd Method for producing glycolate
CN104262152A (en) * 2014-09-16 2015-01-07 上海华谊（集团）公司 Production method of methyl glycolate
CN104923219A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824997A (en) * 1988-01-25 1989-04-25 Monsanto Company Method for preparation of alkyl glycolates
JP2004331531A (en) * 2003-05-02 2004-11-25 Ube Ind Ltd Method for producing glycolate
CN104923219A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof
CN104262152A (en) * 2014-09-16 2015-01-07 上海华谊（集团）公司 Production method of methyl glycolate

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