CN112209826A - Method for preparing aldehyde acetate by glycolate dehydrogenation - Google Patents
Method for preparing aldehyde acetate by glycolate dehydrogenation Download PDFInfo
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- 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
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- 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
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Abstract
The invention provides a method for preparing aldehyde acetate by glycolate dehydrogenation, which comprises the step of reacting raw material glycolate in the presence of a dehydrogenation catalyst to generate aldehyde acetate, wherein the reaction is carried out under the oxygen-free condition. The reaction of this application is reacted under anaerobic condition, has effectively avoided the further oxidation reaction of aldehyde group acetate, has improved aldehyde group acetate's yield.
Description
Technical Field
The invention relates to a method for preparing aldehyde acetate by glycolate dehydrogenation.
Background
The aldehyde acetate has the chemical properties of aldehyde and ester, can perform various reactions, and can be particularly hydrolyzed to prepare formaldehyde formic acid. Formaldehyde formic acid is an organic intermediate for synthesizing spices, medicines, foods, varnish raw materials, dyes, plastic additives and the like, can be used for producing oral vanillin, mandelic acid, allantoin and the like, and therefore the consumption of formaldehyde formic acid is always increased at home and abroad.
Formaldehyde formic acid production methods vary from starting material to starting material, and currently there are about more than ten. 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 formaldehyde formic acid industry has two major problems, one is that the supply of large-batch and high-quality formaldehyde formic acid is insufficient, so that the price advantage of downstream products cannot be fully exerted, and the market development of the formaldehyde formic acid and the downstream products thereof is seriously influenced; secondly, the formaldehyde formic acid is basically produced by adopting a glyoxal method in China, and the price of the glyoxal and the formaldehyde formic acid is influenced finally due to the fluctuation of the international crude oil price.
China has abundant coal and natural gas resources, but insufficient petroleum resources, so that a method for opening up a non-petroleum route has important strategic significance in China. In the 70 th 20 th century, under the influence of the world petroleum crisis, a great deal of C1 chemical research mainly based on natural gas and coal-based raw materials is carried out in various countries, and related technologies are rapidly developed in the 90 th century, so that a great breakthrough is made particularly in the aspect of researching the production of ethylene glycol by using coal or natural gas as raw materials, and a great deal of process by-product glycolate is generated, so that the development of a non-petroleum route for preparing aldehyde acetate by using glycolate has very high competitiveness.
Disclosure of Invention
The invention provides a method for preparing aldehyde acetate by glycolate dehydrogenation, which comprises the step of reacting raw material glycolate in the presence of a dehydrogenation catalyst to generate aldehyde acetate. The method provided by the invention has the characteristics of high conversion rate of the glycollic acid ester and high selectivity of the aldehyde acetate.
According to a first aspect of the present invention there is provided a process for the dehydrogenation of an aldehyde acetate from a glycolate comprising reacting a glycolate in the presence of a dehydrogenation catalyst to form an aldehyde acetate, wherein the reaction is carried out in the absence of oxygen.
According to a preferred embodiment of the present invention, the oxygen-free expression system has an oxygen volume concentration of less than 0.01%, such as 0.001%, 0.0001%, 0.00001%, 0.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is copper and/or copper oxide, and the auxiliary agent is rare earth element and/or rare earth element oxide; preferably, the active component accounts for 1 to 50 parts by weight; 0.01-10 parts of auxiliary agent in terms of rare earth elements; 40-98.99 parts of carrier.
According to a preferred embodiment of the invention, the rare earth element 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 active component contains both copper and copper oxide, the mass ratio of copper to copper oxide being 0.5-10:1, for example 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1 and any value in between, preferably 2-5: 1.
According to a preferred embodiment of the present invention, the average grain size of the copper or copper oxide crystal grains is 10 to 50nm, and may be, for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm and any value therebetween, and is preferably 15 to 35 nm.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst comprises, in parts by weight, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts of active component and any value therebetween, preferably 3 to 35 parts; the auxiliary agent can 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 between the parts, preferably 0.1-7 parts, calculated by rare earth elements; the carrier 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, and is preferably 58 to 96.9 parts.
According to a preferred embodiment of the present invention, the reaction is carried out under a gauge pressure of 0 to 1.5 MPa. For example, the reaction can be carried out under the conditions of 0MPa, 0.1MPa, 0.3MPa, 0.5MPa, 0.7MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.3MPa, 1.5MPa and any value therebetween, preferably 0 to 0.6 MPa.
According to a preferred embodiment of the present invention, the temperature of the reaction is 200-500 deg.C, and may be, for example, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 500 deg.C and any value therebetween, preferably 200-400 deg.C.
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-1For 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-1And 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 invention, nitrogen is added as a diluent gas to the raw materials in the reaction, and the volume space velocity of the nitrogen is preferably 500--1. For example, it may be 500h-1、1000h-1、1500h-1、2000h-1、2500h-1、3000h-1、3500h-1、4000h-1、4500h-1、5000h-1And any value in between, preferably 1000--1。
According to a preferred embodiment of the present invention, the aldehyde acetate is aldehyde methyl acetate, or aldehyde ethyl acetate.
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 salts of the active component and soluble salts of the auxiliary agent;
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 are prepared into solution III as a precipitating agent;
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 drying a filter cake obtained after filtering and washing the slurry IV at 80-120 ℃, roasting at 300-500 ℃, and reducing to obtain the dehydrogenation catalyst.
According to a preferred embodiment of the invention, the soluble salt of the active ingredient 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.
The reaction for preparing the formaldehyde formate by oxidizing the glycolate is a series reaction, and after the glycolate is oxidized to generate the aldehyde acetate, if the reaction is continued, the aldehyde in the aldehyde acetate is further oxidized to carboxyl, and then the aldehyde acetate is further oxidized, a large amount of carbon dioxide and water are generated, and the two reactions both can cause the yield of the aldehyde acetate to be reduced. The reaction of this application is reacted under anaerobic condition, has effectively avoided the further oxidation reaction of aldehyde group acetate, has improved aldehyde group acetate's yield.
In the reaction of preparing aldehyde acetate from glycolate, neither the raw material glycolate nor the product 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 the aldehyde acetate. The dehydrogenation catalyst used in the method is applied to the reaction of preparing aldehyde acetate from glycolate, the reaction can be promoted because the active component copper has certain hydrogen adsorption capacity, and in addition, the rare earth element auxiliary agent is selected to cooperatively regulate the acidity and alkalinity of the catalyst, so that the reaction activity can be improved, the reaction temperature can be reduced, the decomposition and polymerization of glycolate at high temperature can be better inhibited, and the yield of aldehyde acetate can be improved.
By adopting the method, the conversion rate of the glycolate can reach 92.66%, the selectivity of the aldehyde acetate can reach 96.74% 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 solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, and the glycolate dehydrogenation catalyst is obtained after reduction for 12 hoursC1A, and taking a catalyst sample to perform X-fluorescence (XRF) and XRD tests, and the results are shown in Table 1.
Catalyst preparation example 2
1 liter of a solution I containing 0.23mol/L of copper nitrate and 0.018mol/L of lanthanum nitrate is added with 81.5g of an 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 1000m3.h-1/m3Under 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 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 1000m3.h-1/m3Under 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 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 airspeed of 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C4A is obtained after the glycolate dehydrogenation catalyst is reduced for 12 hours, and a catalyst sample is takenX-fluorescence (XRF) and XRD measurements were made, the results are shown in Table 1.
Catalyst preparation example 5
1 liter of solution I containing 0.72mol/L of copper 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 1000m3.h-1/m3Under 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 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 1000m3.h-1/m3Under 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 0.36mol/L of copper 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C7A is obtained after reduction for 48 hours, and a catalyst sample is taken for X-fluorescence (XRF) and XRD detectionThe results of the tests are shown in Table 1.
Catalyst preparation example 8
1 liter of solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C8A is obtained after 5 hours of reduction, 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 9
1 liter of solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under 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 a solution I containing 0.36mol/L of copper nitrate and 0.018mol/L of cerium nitrate is added with 72.5g of an 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C10A 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 11
Taking 1 liter of solution I containing 0.36mol/L copper nitrate and 0.017mol/L 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 1000m3.h-1/m3Under 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, 0.0085mol/L of lanthanum nitrate and 0.0085mol/L of 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 1000m3.h-1/m3Under 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
1 liter of solution I containing 0.36mol/L of copper nitrate and 0.00073mol/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 1000m3.h-1/m3Under 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 result shows thatTable 1.
Catalyst preparation example 14
1 liter of solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under 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 15
Taking 1 liter of solution I containing 0.36mol/L of copper nitrate and 0.0011mol/L of lanthanum 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C15A 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 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 1000m3.h-1/m3Under 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 a solution I containing 0.36mol/L of copper nitrate and 0.018mol/L of lanthanum nitrate was added to 72.5g of a titania 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 1000m3.h-1/m3Under 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 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 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 1000m3.h-1/m3Under 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 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 1000m3.h-1/m3Under 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 solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under 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 a solution I containing 0.36mol/L of copper nitrate and 0.018mol/L of lanthanum nitrate is added with stirring to the solution I with 72.5g of ZSM-5 carrier having a silica-alumina ratio of 150 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 1000m3.h-1/m3Under the condition, the temperature is programmed to 300 ℃, the glycolate dehydrogenation catalyst C21A 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 22
1 liter of solution I containing 0.36mol/L of copper 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 1000m3.h-1/m3Under the condition, 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 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 600 ℃, and using hydrogen at a volume airspeed of 1000m3.h-1/m3Under 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 solution I containing 0.36mol/L of copper 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 400 ℃, and using hydrogen at a volume airspeed of 1000m3.h-1/m3Under the condition, 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 25
1 liter of solution I containing 0.36mol/L of copper 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 500 ℃, and using hydrogen at a volume airspeed of 1000m3.h-1/m3Under 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 comparative example 1
A solution was prepared in the same manner as in example 1, except that no auxiliary agent was added, i.e., 1 liter of a solution containing 0.36mol/L of copper nitrate was used as the solution I, and 72g of an alumina carrier was added to the solution I 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 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.
TABLE 1
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%. Methyl glycolate is used as a raw material, the reaction temperature is 290 ℃, the reaction pressure is 0.1MPa, and the hourly space velocity of the raw material liquid is 0.4 hour-1Nitrogen volume space velocity of 1000 hours-1The catalysts were evaluated under the conditions and the reaction results are shown in Table 2.
TABLE 2
Application example 2
A reaction for producing formylacetic acid methyl ester by reacting methyl glycolate was carried out by the method of application example 1 using the catalyst in catalyst preparation example 1, except that the conditions, condition parameters and experimental results of the reaction were changed as shown in Table 3.
TABLE 3
Application example 3
Aldehyde ethyl acetate was prepared by a reaction using ethyl glycolate as a raw material using 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
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 preparing aldehyde acetate by glycolate dehydrogenation comprises the step of reacting raw glycolate in the presence of a dehydrogenation catalyst to generate aldehyde acetate, wherein the reaction is carried out under the oxygen-free condition.
2. The method of claim 1, wherein the dehydrogenation catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is copper and/or an oxide of copper, and the auxiliary agent is a rare earth metal and/or an oxide of a rare earth metal; preferably, the active component accounts for 1 to 50 parts by weight, preferably 3 to 35 parts by weight; 0.01-10 parts of assistant, preferably 0.1-7 parts of rare earth element; the carrier is 40-98.99 parts, preferably 58-96.9 parts.
3. The method of claim 2, wherein the rare earth element is selected from one or more of lanthanum, cerium, and samarium.
4. The process of claim 2 or 3, wherein the support is selected from one or more of silica, alumina, zirconia, titania and silica alumina molecular sieves, preferably one or more of alumina, SBA-15, MCM-41 and ZSM-5 molecular sieves.
5. The method according to any one of claims 2 to 4, wherein the active component contains both copper and copper oxide, the mass ratio of copper to copper oxide being 0.5-10: 1; preferably, the copper or copper oxide crystal grains have an average particle diameter of 10 to 50nm, preferably 15 to 35 nm.
6. The process according to any one of claims 1 to 5, characterized in that the glycolate reaction is carried out under conditions of 0-1.5MPa, preferably 0-0.6 MPa.
7. The process according to any one of claims 1 to 6, characterized in that the temperature of the glycolic acid ester reaction is 200-500 ℃, preferably 200-400 ℃.
8. The process according to any one of claims 1 to 7, characterized in that the mass space velocity of the glycolic acid ester is between 0.1 and 2.5h-1Preferably 0.1 to 2h-1。
9. The process as claimed in any one of claims 1 to 8, wherein nitrogen is added as a diluent gas to the glycolic acid ester, preferably at a volume space velocity of 500--1。
10. The method according to any one of claims 1 to 9, wherein the aldehyde acetate is methyl aldehyde acetate and/or ethyl aldehyde acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340748A (en) * | 1979-02-08 | 1982-07-20 | Hoechst Aktiengesellschaft | Process for the manufacture of glyoxylic acid esters |
| CN104043455A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparation of glycol by oxalate hydrogenation |
| 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 |
| CN107445833A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The method of ethyl glycolate oxidation synthesis glyoxylate ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340748A (en) * | 1979-02-08 | 1982-07-20 | Hoechst Aktiengesellschaft | Process for the manufacture of glyoxylic acid esters |
| CN104043455A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparation of glycol by oxalate hydrogenation |
| 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 |
| CN107445833A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The method of ethyl glycolate oxidation synthesis glyoxylate ester |
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