CN112209818B - Method for preparing glyoxylic acid ester from glycolic acid ester - Google Patents

Method for preparing glyoxylic acid ester from glycolic acid ester Download PDF

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CN112209818B
CN112209818B CN201910630455.4A CN201910630455A CN112209818B CN 112209818 B CN112209818 B CN 112209818B CN 201910630455 A CN201910630455 A CN 201910630455A CN 112209818 B CN112209818 B CN 112209818B
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slurry
filter cake
acid ester
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CN112209818A (en
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龚海燕
张旭
钟源
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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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention provides a method for preparing glyoxylate from glycolate, which comprises the step of reacting glycolate in the presence of a dehydrogenation catalyst to generate glyoxylate, wherein the dehydrogenation catalyst comprises the following components in parts by weight: a) 1-50 parts of copper and zinc; b) 0.01-10 parts of rare earth metal and/or rare earth metal oxide calculated by rare earth element; c) 40-98.99 parts of carrier. By adopting the method, the conversion rate of the glycolate can reach 94 percent, the selectivity of the glycolate can reach 98 percent at most, and a better technical effect is achieved.

Description

Method for preparing glyoxylic acid ester from glycolic acid ester
Technical Field
The invention relates to a method for preparing glyoxylic acid ester from glycolic acid 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 perfumes, medicines, foods, varnish raw materials, dyes, plastic additives and the like, can be used for producing vanillin, mandelic acid, allantoin and the like for oral administration, 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 glyoxylic acid industry has two major problems, one is that 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, and the price of the glyoxal and the price of the glyoxalic acid are influenced by the international price fluctuation of crude oil.
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 developed 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 using the glycolate has very high competitiveness.
Disclosure of Invention
The invention provides a method for preparing glyoxylic acid ester from glycolic acid ester, which comprises the step of reacting glycolic acid ester to generate glyoxylic acid ester in the presence of a dehydrogenation catalyst. The method provided by the invention has the characteristics of high conversion rate of the glycolate and high selectivity of the glyoxylate.
According to a first aspect of the invention, a method for preparing glyoxylate from glycolate is provided, which comprises reacting glycolate in the presence of a dehydrogenation catalyst to generate glyoxylate, wherein the dehydrogenation catalyst comprises a carrier, active components and auxiliaries, the active components are copper and zinc, and the auxiliaries are rare earth elements and/or oxides of the rare earth elements.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst comprises the following components in parts by weight:
a) 1-50 parts of copper and zinc;
b) 0.01-10 parts of rare earth metal and/or rare earth element oxide in terms of rare earth element;
c) 40-98.99 parts of carrier.
According to a preferred embodiment of the invention, the reaction is carried out under conditions of-0.1 to 0.5MPa in gauge pressure, for example, -0.1MPa, -0.09MPa, -0.08MPa, -0.07MPa, -0.06MPa, -0.05MPa, -0.04MPa, -0.03MPa, -0.02MPa, -0.01MPa, 0MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa and any value therebetween, preferably-0.1 to 0MPa. The reaction for preparing the glyoxylic ester by the glycollic ester dehydrogenation is a reaction with increased volume, so the invention can promote the reaction to be carried out under lower pressure and preferably by adopting negative pressure reaction, and the conversion rate of the glycollic ester is improved.
According to a preferred embodiment of the present invention, the temperature of the reaction is 150 to 500 ℃, for example 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 500 ℃ and any value therebetween, preferably 200 to 400 ℃.
According to a preferred embodiment of the invention, the mass space velocity of the starting glycolic acid ester during the reaction is between 0.1 and 2.5h -1 For example, it may be 0.1h -1 、0.5h -1 、1.0h -1 、1.2h -1 、1.5h -1 、1.7h -1 、2.0h -1 、2.5h -1 And any value in between, preferably 0.1-2h -1 。
According to the preferred embodiment of the present invention, the reaction is carried out under the condition of no oxygen, and the prior art shows that the addition of oxygen or oxygen-containing gas to the reaction raw materials is advantageous for the reaction, but the inventors of the present application have surprisingly found that the reaction is more advantageous to be carried out under the condition of no oxygen in the reaction system of the present application.
According to a preferred embodiment of the present invention, nitrogen is added as a diluent gas to the raw materials in the reaction, and preferably, the volume space velocity of the nitrogen is 500 to 3000h -1 。
According to a preferred embodiment of the invention, the rare earth metal is selected from one or more of lanthanum, cerium and samarium.
According to a preferred embodiment of the present invention, the support is selected from one or more of silica, alumina, zirconia, titania and a silicoaluminophosphate molecular sieve, wherein the molecular sieve is selected from one or more of SBA-15, MCM-41 and ZSM-5.
According to a preferred embodiment of the invention, the support is selected from one or more of alumina, SBA-15, MCM-41 and ZSM-5 molecular sieves.
According to a preferred embodiment of the invention, the molar ratio of copper and zinc in said component a) is between 0.5 and 10:1, 1.5.
According to a preferred embodiment of the present invention, in the dehydrogenation catalyst, the component a) is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts and any value therebetween, preferably 3 to 35 parts, in parts by weight, the component b) may be 0.01 part, 0.05 part, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and any value therebetween, preferably 0.1 to 7 parts, and the component c) may be 40 parts, 45 parts, 50 parts, 55 parts, 58 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 96.9 parts, 98.99 parts and any value therebetween, preferably 58 to 96.9 parts, in parts by weight.
According to a preferred embodiment of the invention, the glyoxylate is methyl glyoxylate or ethyl glyoxylate.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst is prepared by the steps of:
1) Preparing a mixed solution I from soluble salt of the component a) and soluble salt of the component b);
2) Adding the carrier into the solution I under the stirring state to obtain slurry II;
3) One or more of carbonate, bicarbonate, alkali metal hydroxide and inorganic ammonia water is prepared into solution III as precipitant;
4) Adding the solution III into the slurry II, and controlling the pH value of the reaction end point to be 6-8.5 to obtain slurry IV;
5) And (3) filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at the temperature of 80-120 ℃, roasting the filter cake at the temperature of 300-500 ℃, and reducing to obtain the dehydrogenation catalyst.
According to a preferred embodiment of the invention, the soluble salt of component a) is selected from one or more of copper nitrate, copper acetate and copper oxalate.
According to a preferred embodiment of the invention, in said step 3), the carbonate or bicarbonate is selected from carbonates or bicarbonates of alkali metals or alkaline earth metals; the hydroxide of an alkali metal is selected from sodium hydroxide and/or potassium hydroxide; the inorganic ammonia is selected from liquid ammonia or ammonia water.
In the reaction for preparing glyoxylic ester from glycolate, neither raw material methyl glycolate nor product methyl glyoxylate is very stable at high temperature, and reactions such as decomposition polymerization and the like are easy to occur to influence the yield of glyoxylic ester. The dehydrogenation catalyst used in the method is applied to the reaction of preparing the glyoxylic ester from the glycolic acid ester, the active components of copper and zinc have certain hydrogen adsorption capacity, the reaction can be promoted, and in addition, the rare earth element auxiliary agent is selected to synergistically regulate the acid-base property of the catalyst, so that the reaction activity can be improved, the decomposition and polymerization of the glycolic acid ester at high temperature can be better inhibited, and the yield of the glyoxylic acid ester is improved.
By adopting the method, the conversion rate of the glycolate can reach more than 95 percent, the selectivity of the glycolate can reach more than 98 percent at most, 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.
Catalyst preparation example 1
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C1A is obtained after reduction for 12 hours, and a catalyst sample is taken as X-fluorescence (XR)F) And XRD testing, the results are shown in table 1.
Catalyst preparation example 2
1 liter of a solution I containing 0.23mol/L of copper nitrate, 0.045mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 81.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C2A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 3
1 liter of solution I containing 0.50mol/L of copper nitrate, 0.097mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 63g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C3A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 4
1 liter of a solution I containing 0.045mol/L of copper nitrate, 0.087mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 94.4g of alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume space velocity of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, and the glycolate is obtained after reduction for 12 hoursFor agent C4A, a sample of the catalyst was taken for X-fluorescence (XRF) and XRD measurements, the results of which are shown in Table 1.
Catalyst preparation example 5
1 liter of solution I containing 0.72mol/L of copper nitrate, 0.14mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 48g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C5A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1. Catalyst preparation example 6
1 liter of solution I containing 0.017mol/L of copper nitrate, 0.0033mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 96.3g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C6A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 7
1 liter of solution I containing 0.39mol/L of copper nitrate, 0.038mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, and the glycolate dehydrogenation is obtained after the glycolate is reduced for 48 hoursCatalyst C7A, a sample of the catalyst was taken for X-fluorescence (XRF) and XRD measurements, the results of which are shown in Table 1.
Catalyst preparation example 8
1 liter of solution I containing 0.28mol/L of copper nitrate, 0.14mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume space velocity of 1000m 3 .h -1 /m 3 Under the conditions, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C8A is obtained after reduction for 5 hours, and a catalyst sample is taken for X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 9
1 liter of a solution I containing 0.14mol/L of copper nitrate, 0.28mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 200 ℃, the glycolate dehydrogenation catalyst C9A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 10
1 liter of solution I containing 0.38mol/L of copper nitrate, 0.047mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 200 ℃, and the reduction is carried out for 12 hoursThen, the glycolate dehydrogenation catalyst C10A is obtained, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 11
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.070mol/L of zinc nitrate and 0.018mol/L of cerium nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C11A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 12
Taking 1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.017mol/L of samarium nitrate, and adding 72.5g of alumina carrier into the solution I under the stirring state to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C12A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 13
Taking 1 liter of solution I containing 0.36mol/L copper nitrate, 0.07mol/L zinc nitrate, 0.0085mol/L lanthanum nitrate and 0.0085mol/L cerium nitrate, and adding 72.5g of alumina carrier into the solution I under the stirring state to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C13A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 14
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.00073mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the conditions, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C14A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 15
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.072mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C14A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 16
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.0011mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, and roasting the filter cake at 450 DEG CHydrogen at a volume space velocity of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C16A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 17
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.05mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C17A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 18
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate was added to 72.5g of a titanium oxide carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume space velocity of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C18A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 19
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate was added to 72.5g of a zirconia carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IVDrying the obtained filter cake at 100 ℃, roasting at 450 ℃, and using hydrogen at a volume space velocity of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C19A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 20
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate was added to the solution I with stirring 72.5g of SBA-15 carrier to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C20A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 21
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of MCM-41 carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the conditions, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C21A is obtained after reduction for 12 hours, and a catalyst sample is taken for X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 22
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of ZSM-5 carrier with a silica-alumina ratio of 150 to the solution I under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end pointIs 7.0, and slurry IV is obtained; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the conditions, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C22A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 23
1 liter of solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of alumina carrier under stirring to obtain slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 300 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C23A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 24
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 600 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C24A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 25
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Using 3mol/L ammonium bicarbonate solution as precipitant III under stirringAdding the slurry II, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 400 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C25A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 26
1 liter of a solution I containing 0.36mol/L of copper nitrate, 0.07mol/L of zinc nitrate and 0.018mol/L of lanthanum nitrate is added with 72.5g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7.0 to obtain slurry IV; filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 500 ℃, and using hydrogen at a volume airspeed of 1000m 3 .h -1 /m 3 Under the conditions, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C26A is obtained after reduction for 12 hours, and a catalyst sample is taken to carry out X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation comparative example 1
A solution was prepared in the same manner as in example 1, except that no auxiliary agent was added, that is, 1 liter of a solution I containing 0.36mol/L copper nitrate and 0.07mol/L zinc nitrate, and 72g of an alumina carrier was added to the solution I under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7 to obtain slurry IV; and filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃ to obtain the glycolate dehydrogenation catalyst C1B, and taking a catalyst sample to perform X-fluorescence (XRF) and XRD tests, wherein the results are shown in Table 1.
Catalyst preparation comparative example 2
A solution was prepared in the same manner as in example 1 except that the concentrations of active components were changed by adding 72.5g of an alumina carrier to the solution I under stirring in 1 liter of a solution I containing 0.007mol/L copper nitrate and 0.018mol/L lanthanum nitrate to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7 to obtain slurry IV; and filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃ to obtain the glycolate dehydrogenation catalyst C2B, and taking a catalyst sample to perform X-fluorescence (XRF) and XRD tests, wherein the results are shown in Table 1.
Catalyst preparation comparative example 3
A solution was prepared in the same manner as in example 1 except that Bi was used as an auxiliary, that is, 1 liter of a solution I containing 0.34mol/L copper nitrate and 0.012mol/L bismuth nitrate was added to 72g of an alumina carrier under stirring to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7 to obtain slurry IV; and filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃ to obtain the glycolate dehydrogenation catalyst C3B, and taking a catalyst sample to perform X-fluorescence (XRF) and XRD tests, wherein the results are shown in Table 1.
Catalyst preparation comparative example 4
A solution was prepared in the same manner as in example 1 except that the ratio of copper nitrate to zinc nitrate was changed by adding 72g of an alumina carrier to 1 liter of a solution I containing 0.07mol/L copper nitrate, 0.35mol/L zinc nitrate and 0.018mol/L lanthanum nitrate to obtain a slurry II. Adding 3mol/L ammonium bicarbonate solution serving as a precipitator III into the slurry II under stirring, and controlling the pH value of the reaction end point to be 7 to obtain slurry IV; and filtering and washing the slurry IV to obtain a filter cake, drying the filter cake at 100 ℃, roasting the filter cake at 450 ℃ to obtain the glycolate dehydrogenation catalyst C4B, and taking a catalyst sample to perform X-fluorescence (XRF) and XRD tests, wherein the results are shown in Table 1.
TABLE 1
Figure BDA0002128513450000121
Figure BDA0002128513450000131
Application example 1
The catalysts obtained in catalyst preparation examples 1 to 25 and catalyst preparation comparative examples 1 to 3 were subjected to reaction evaluation. First, the catalysts prepared in catalyst preparation examples 1 to 25 and catalyst preparation comparative examples 1 to 3 were charged into a reactor, respectively, and the reaction system was replaced with nitrogen gas, and the replacement was stopped by detecting that the oxygen gas volume concentration was less than 0.01%. Using methyl glycolate as a raw material, and reacting at 290 ℃ under-0.06 MPa at a raw material liquid hourly space velocity of 0.4 h -1 Nitrogen gas volume space velocity 1000 hours -1 The catalysts were evaluated under the conditions and the reaction results are shown in Table 2.
TABLE 2
Figure BDA0002128513450000132
Figure BDA0002128513450000141
Application example 2
The reaction of methyl glycolate to methyl glyoxylate was carried out using the catalyst of catalyst preparation example 1 in accordance with the procedure of application example 1, except that the conditions, the parameters of the conditions, and the results of the experiment were changed as shown in Table 3.
TABLE 3
Figure BDA0002128513450000142
Application example 3
The reaction for producing methyl glyoxylate by the reaction of methyl glycolate with the catalyst of catalyst preparation example 1 was carried out in accordance with the procedure of application example 1 except that the reaction pressure during the reaction of methyl glycolate was 0.8MPa. Analysis showed methyl glycolate conversion of 86.15% and methyl glyoxylate selectivity of 92.19%.
Application example 4
Ethyl glyoxylate was prepared by reacting ethyl glycolate as a starting material with the catalyst prepared in catalyst preparation example 1 in the same manner as in application example 1. The results are shown in Table 4.
TABLE 4
Figure BDA0002128513450000151
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. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made 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 (14)

1. A method for preparing glyoxylic acid ester from glycolic acid ester comprises the step of reacting glycolic acid ester in the presence of a dehydrogenation catalyst to generate glyoxylic acid ester, wherein the dehydrogenation catalyst comprises the following components in parts by weight:
a) 3-35 parts of copper and zinc;
b) 0.1-7 parts of rare earth metal and/or rare earth metal oxide calculated by rare earth element;
c) 58-96.9 parts of a carrier;
the molar ratio of copper to zinc in component a) is 2-8; the rare earth element is selected from one or more of lanthanum, cerium and samarium;
the average grain size of copper and zinc is 10-50nm.
2. The process according to claim 1, wherein the reaction is between-0.1 and 0.5MPa.
3. The process of claim 2, wherein the reaction is between-0.1 and 0MPa.
4. The process according to claim 1, characterized in that the temperature of the glycolic acid ester reaction is 150-500 ℃.
5. The process according to claim 4, characterized in that the temperature of the glycolic acid ester reaction is 200-400 ℃.
6. The process according to claim 1, wherein nitrogen is added as a diluent gas to the glycolic acid ester in the reaction.
7. The method of claim 6, wherein the volume space velocity of the nitrogen gas is 500-3000h -1 。
8. The method as claimed in claim 1, wherein the mass space velocity of the glycolic acid ester is 0.1-2.5h -1 。
9. The process according to claim 8, wherein the mass space velocity of the glycolic acid ester is 0.1-2h -1 。
10. The process of claim 1, wherein the reaction is carried out in the absence of oxygen.
11. A method as claimed in claim 1, characterized in that the grain size of copper and zinc is 15-35nm on average.
12. The process of claim 1, wherein the support is selected from one or more of silica, alumina, zirconia, titania and a silica alumina molecular sieve.
13. The process of claim 12, wherein the support is one or more of alumina, SBA-15, MCM-41, and ZSM-5 molecular sieves.
14. The method according to any one of claims 1 to 13, wherein the glyoxylate is methyl glyoxylate or ethyl glyoxylate.
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CN107445827A (en) * 2016-05-30 2017-12-08 中国石油化工股份有限公司 The method of ethyl glycolate oxidative dehydrogenation glyoxylic ester
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US4340748A (en) * 1979-02-08 1982-07-20 Hoechst Aktiengesellschaft Process for the manufacture of glyoxylic acid esters
CN85101409A (en) * 1984-01-14 1987-01-24 赫彻斯特股份公司 The processing method of preparation hydrated glyoxylate
US4968833A (en) * 1984-01-14 1990-11-06 Hoechst Aktiengesellschaft Process for the preparation of a glyoxylic acid ester
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