CN117960192A

CN117960192A - Oxidative dehydrogenation catalyst, preparation method and application thereof, and method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate

Info

Publication number: CN117960192A
Application number: CN202211321661.5A
Authority: CN
Inventors: 山炜巍; 施春辉; 王群; 肖本端
Original assignee: Guangxi Huayi Energy Chemical Co ltd; Shanghai Huayi Energy Chemical Co ltd
Current assignee: Guangxi Huayi Energy Chemical Co ltd; Shanghai Huayi Energy Chemical Co ltd
Priority date: 2022-10-26
Filing date: 2022-10-26
Publication date: 2024-05-03

Abstract

The invention provides an oxidative dehydrogenation catalyst, a preparation method and application thereof, and a method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate. The oxidative dehydrogenation catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is an oxygen-containing compound of iron, and the auxiliary agent is a compound of at least one metal element selected from tungsten, vanadium, cobalt, nickel, molybdenum, zinc and antimony. The preparation method of the catalyst comprises the following steps: 1) Adding a precipitant solution into a first slurry comprising a salt of an iron element in the active component and a carrier until the pH value of the mixed solution is 4.1-8, and adding a soluble salt solution comprising a metal element in the auxiliary agent; 2) Aging and filtering the second slurry; 3) And drying and roasting the filter cake. The oxidative dehydrogenation catalyst is used for oxidative dehydrogenation reaction of hydroxyacetate and oxygen-containing gas. The oxidative dehydrogenation catalyst is used for synthesizing the aldehyde acetate through oxidative dehydrogenation of the hydroxyacetate, and has the advantages of small airspeed and high yield of the aldehyde acetate.

Description

Oxidative dehydrogenation catalyst, preparation method and application thereof, and method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate

Technical Field

The invention relates to the technical field of oxidative dehydrogenation, in particular to an oxidative dehydrogenation catalyst, a preparation method and application thereof, and a method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate.

Background

The aldehyde acetate can generate various reactions due to the chemical properties of aldehyde and ester, is an important synthetic intermediate, has wide application in the fields of medicine, fuel, chemical industry and the like, particularly has active chemical properties, can simultaneously generate the reaction of aldehyde and acid and cyclization and condensation reaction, and has wide application, and is an important high-added-value organic intermediate for synthesizing perfume, medicine, dye, plastic additives and the like. The synthesis method of the aldehyde acetate is various, and the tartrate oxidation method, the maleic acid ozone oxidation method, the butenedioic acid diethyl ester oxidation method and the like are adopted. The processes have the limitations of large waste liquid amount, high pressure, long flow and the like.

The resources in China are characterized by shortage of petroleum resources and insufficient natural gas resources, but rich in coal resources. With the deep research of C1 chemistry in China, the related chemical production technology is developed at a high speed. In recent years, along with the promotion of China, the process route of preparing ethylene glycol by using coal as a raw material oxalate is gradually mature, and the main process route of coal-based ethylene glycol in China is developed. Along with the fluctuation of international oil price, the petrochemical line ethylene glycol continuously compresses the profit margin of the coal-based line ethylene glycol. In order to improve the competitiveness of a coal-to-ethylene glycol device, part of enterprises rely on the device, expand dimethyl oxalate derivative products, enrich the variety of the products of the enterprises, improve the risk resistance, improve the selectivity of hydroxyacetate in the products by controlling the hydrogenation process of dimethyl oxalate, make the most of the significance of reasonably and efficiently utilizing the hydroxyacetate to improve the technological benefit of preparing the ethylene glycol from synthetic gas, and obviously improve the competitiveness by continuously developing a coal-based route to prepare the aldol acetate through oxidative dehydrogenation of the hydroxyacetate.

In the oxidative dehydrogenation process of the hydroxyacetate, after the hydroxyacetate is dehydrogenated and oxidized into aldehyde group, if the oxidation degree is not controlled, the hydroxyacetate can be continuously oxidized into carboxyl group so as to decompose and generate a large amount of carbon dioxide and water, and the yield of target products is influenced, so that in the process of preparing the aldol acetate by oxidative dehydrogenation of the hydroxyacetate, a proper oxidative dehydrogenation catalyst is required to be selected so as to improve the selectivity of the aldol acetate. At present, patent reports are made on the catalyst in China, for example, CN107445832B discloses a catalyst prepared by taking iron or iron oxide as an active component and adding a certain amount, wherein under the conditions that the reaction temperature is 120 ℃, the oxygen-ester ratio is 0.8, the reaction pressure is 0.2MPa, the space velocity of ethyl glycolate is 1h ^-1, the maximum conversion rate of methyl glycolate is 97.73 percent, and the yield of methyl glyoxylate is 91.92 percent. However, in the preparation process of the catalyst, multiple steps such as aging, drying, dipping, re-drying, roasting and the like are needed, the catalyst preparation steps are multiple, the oyster duration is long, and the catalyst auxiliary agent covers the surface of the catalyst by a single dipping method, so that a synergistic effect cannot be generated with active components in the catalyst, and the effect of the auxiliary agent in the catalyst is reduced.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide an oxidative dehydrogenation catalyst, a preparation method and application, and a method for synthesizing an aldehyde acetate by oxidative dehydrogenation of a hydroxyacetate, wherein the oxidative dehydrogenation catalyst is used in the synthesis of an aldehyde acetate by oxidative dehydrogenation of a hydroxyacetate, and has a small space velocity and a high yield of an aldehyde acetate.

To achieve the above and other related objects, a first aspect of the present invention provides an oxidative dehydrogenation catalyst comprising an active component, an auxiliary agent, and a carrier, wherein the active component is an oxygen-containing compound of iron, and the auxiliary agent is a compound of at least one metal element selected from tungsten, vanadium, cobalt, nickel, molybdenum, zinc, and antimony.

Preferably, the method further comprises at least one of the following technical characteristics:

a1 The carrier is selected from at least one of silicon oxide, aluminum oxide and silicon-aluminum molecular sieve;

a2 1 to 40 parts by weight of iron element in the active component, such as 1 to 5 parts by weight, 5 to 10 parts by weight, 10 to 15 parts by weight, 15 to 17 parts by weight, 17 to 20 parts by weight, 20 to 23 parts by weight, 23 to 25 parts by weight or 25 to 40 parts by weight, 1 to 20 parts by weight, such as 1 to 2 parts by weight, 2 to 3 parts by weight, 3 to 4 parts by weight, 4 to 5 parts by weight, 5 to 5.2 parts by weight, 5.2 to 6.5 parts by weight, 6.5 to 10 parts by weight, 10 to 12 parts by weight or 12 to 20 parts by weight, 40 to 98 parts by weight, such as 40 to 59 parts by weight, 59 to 63 parts by weight, 63 to 74 parts by weight, 74 to 75 parts by weight, 75 to 77 parts by weight, 77 to 79 parts by weight, 79 to 79.8 parts by weight, 79.8 to 83.5 to 85 parts by weight, 85 to 85 parts by weight or 85 to 94 parts by weight or 94 to 98 parts by weight.

More preferably, in the feature a 3), the iron element in the active component is 5-25 parts, the metal element in the auxiliary agent is 1-12 parts, and the carrier is 63-94 parts.

The second aspect of the present invention provides a method for preparing the oxidative dehydrogenation catalyst, comprising the steps of:

1) Adding a precipitant solution into the first slurry containing the salt of the iron element in the active component and the carrier until the pH value of the mixed solution is 4-8, such as 4-4.1, 4.1-4.5, 4.5-4.7, 4.7-5, 5-5.4, 5.4-6.2 or 6.2-8, adding a soluble salt solution containing the metal element in the auxiliary agent until the precipitation reaction is ended, and obtaining a second slurry;

2) Aging and filtering the second slurry to obtain a filter cake;

3) And drying and roasting the filter cake to obtain the oxidative dehydrogenation catalyst.

11 In step 1), the precipitant is at least one selected from alkali metal hydrogencarbonates, hydroxides and ammonia water, such as at least one of sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide and potassium hydroxide;

12 In step 1), the pH value of the end point of the precipitation reaction is 7 to 10, such as 7 to 7.8, 7.8 to 8.3, 8.3 to 8.5, 8.5 to 8.8, 8.8 to 9 or 9 to 10;

13 In step 1), the temperature of the precipitation reaction is 70 to 110 ℃, such as 70 to 80 ℃, 80 to 90 ℃ or 90 to 110 ℃, more preferably 90 to 100 ℃;

14 In step 1), the first slurry is obtained by: mixing a salt solution including iron element in the active component with a carrier;

21 In step 2), the aging temperature is 85 to 120 ℃, such as 85 to 90 ℃, 90 to 100 ℃ or 100 to 120 ℃, preferably 85 to 100 ℃;

22 In step 2), the aging time is 1 to 12 hours, such as 1 to 3 hours, 3 to 4 hours, 4 to 5 hours, 5 to 6 hours or 6 to 12 hours, preferably 3 to 6 hours;

23 In the step 2), filtering and then washing with desalted water to obtain a filter cake;

31 In step 3), drying is carried out under the nitrogen atmosphere;

32 In step 3), the drying temperature is 90-150 ℃, such as 90-100 ℃, 100-110 ℃, 110-120 ℃ or 120-150 ℃;

33 In step 3), roasting is carried out under an air atmosphere;

34 In step 3), the baking temperature is 350-600 ℃, such as 350-430 ℃, 430-450 ℃, 450-500 ℃ or 500-600 ℃.

In a third aspect, the present invention provides the use of the above oxidative dehydrogenation catalyst for the oxidative dehydrogenation of hydroxyacetate with a molecular oxygen-containing gas to obtain an aldol acetate.

b1 In a fixed bed tubular reactor;

b2 Oxygen molecules from pure oxygen or air;

b3 The molecular oxygen-containing gas further comprises at least one of N ₂ and CO ₂;

b4 The mass airspeed of the hydroxyacetate is 0.2 to 5h ^-1, such as 0.2 to 0.3, 0.3 to 0.5h ^-1、0.5～1h^-1、1～1.5h^-1 or 1.5 to 5h ^-1;

b5 The gas space velocity of the oxygen-containing molecules is 500 to 1000h ^-1, such as 500 to 600h ^-1、600～780h^-1、780～840h^-1、840～900h^-1、900～936h^-1 or 936 to 1000h ^-1;

b6 Molar ratio of oxygen molecules to glycolate in the oxygen molecule-containing gas is (0.1 to 6): 1, such as 0.1 to 0.2, 0.2 to 0.5, 0.5 to 1, 1 to 1.5, 1.5 to 2 or 2 to 6;

b7 The pressure of the oxidative dehydrogenation reaction is 0 to 3Mpa, such as 0 to 0.1Mpa, 0.1 to 0.2Mpa, 0.2 to 0.3Mpa, 0.3 to 0.4Mpa, 0.4 to 0.5Mpa, 0.5 to 0.6Mpa, 0.6 to 1Mpa or 1 to 3Mpa;

b8 The temperature of the oxidative dehydrogenation reaction is 100 to 400 ℃, such as 100 to 110 ℃, 110 to 120 ℃, 120 to 130 ℃, 130 to 150 ℃, 150 to 160 ℃, 160 to 180 ℃, 180 to 200 ℃, 200 to 250 ℃ or 250 to 400 ℃.

In a fourth aspect, the present invention provides a method for synthesizing an aldehyde acetate by oxidative dehydrogenation of a hydroxyacetate, wherein the hydroxyacetate reacts with a molecular oxygen-containing gas to form the aldehyde acetate under the condition of the oxidative dehydrogenation catalyst.

c1 In a fixed bed tubular reactor;

c2 Oxygen molecules from pure oxygen or air;

c3 The molecular oxygen-containing gas further comprises at least one of N ₂ and CO ₂;

c4 The mass airspeed of the hydroxyacetate is 0.2 to 5h ^-1, such as 0.2 to 0.3h ^-1、0.3～0.5h^-1、0.5～1h^-1、1～1.5h^-1 or 1.5 to 5h ^-1;

c5 The gas space velocity of the oxygen-containing molecules is 500 to 1000h ^-1, such as 500 to 600h ^-1、600～780h^-1、780～840h^-1、840～900h^-1、900～936h^-1 or 936 to 1000h ^-1;

c6 Molar ratio of oxygen molecules to glycolate in the oxygen molecule-containing gas is (0.1 to 6): 1, such as 0.1 to 0.2, 0.2 to 0.5, 0.5 to 1, 1 to 1.5, 1.5 to 2 or 2 to 6;

c7 The pressure of the oxidative dehydrogenation reaction is 0 to 3Mpa, such as 0 to 0.1Mpa, 0.1 to 0.2Mpa, 0.2 to 0.3Mpa, 0.3 to 0.4Mpa, 0.4 to 0.5Mpa, 0.5 to 0.6Mpa, 0.6 to 1Mpa or 1 to 3Mpa;

c8 The temperature of the oxidative dehydrogenation reaction is 100 to 400 ℃, such as 100 to 110 ℃, 110 to 120 ℃, 120 to 130 ℃, 130 to 150 ℃, 150 to 160 ℃, 160 to 180 ℃, 180 to 200 ℃, 200 to 250 ℃ or 250 to 400 ℃.

More preferably, at least one of the following technical features is further included:

c41 In the characteristic c 4), the mass airspeed of the hydroxyacetate is 0.3-1.5 h ^-1;

c51 In the characteristic c 5), the gas space velocity of the oxygen-containing molecules is 600 to 900h ^-1;

c61 In the feature c 6), the molar ratio of the oxygen molecules in the oxygen-molecule-containing gas to the glycolate is (0.2 to 2): 1, a step of;

c71 In the c 7), the pressure of the oxidative dehydrogenation reaction is 0-1 Mpa;

c81 In the feature c 8), the temperature of the oxidative dehydrogenation reaction is from 100 to 250 ℃.

The technical scheme has at least one of the following beneficial effects:

1) The active components and the auxiliary agent in the oxidative dehydrogenation catalyst are uniformly distributed.

2) The oxidative dehydrogenation catalyst is used for synthesizing the aldehyde acetate by oxidative dehydrogenation of the hydroxyacetate, and the yield of the aldehyde acetate is high.

3) Under the condition of the oxidative dehydrogenation catalyst, the hydroxyacetate and the gas containing oxygen molecules are subjected to oxidative dehydrogenation reaction to obtain the aldehyde acetate, the space velocity is small, and the yield of the aldehyde acetate is high.

4) The preparation method of the oxidative dehydrogenation catalyst has the characteristics of short flow and high preparation efficiency, and the prepared oxidative dehydrogenation catalyst is used for synthesizing the aldehyde acetate by oxidative dehydrogenation of the hydroxyacetate, so that the yield of the aldehyde acetate is high.

Detailed Description

The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.

Example 1

100Ml of a solution I containing 1.79mol/L ferric nitrate was prepared, and 83.5g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 50ml of a solution IV containing 0.42mol/L ammonium molybdate hydrate, 1.58mol/L ammonium metavanadate and 0.06mol/L ammonium tungstate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 1.5mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 8.3, aging at 90 ℃ for 5 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst A1, wherein the weight parts of the components are shown in the table 1.

The catalyst A1 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 840h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.5, the catalyst is contacted and reacted under the conditions of the reaction temperature of 180 ℃, the reaction pressure of 0.6MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 2

200Ml of a solution I containing 1.34mol/L ferric nitrate was prepared, and 79.8g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 30ml of a solution IV containing 0.7mol/L ammonium molybdate hydrate, 1.96mol/L ammonium metavanadate and 0.03mol/L ammonium tungstate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.7, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 8.5, aging at 90 ℃ for 4 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 500 ℃ in an air atmosphere to obtain the catalyst A2, wherein the weight parts of the components are shown in the table 1.

The catalyst A2 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 840h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.5, the catalyst is contacted and reacted under the conditions of the reaction temperature of 150 ℃, the reaction pressure of 0.4MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 3

75Ml of a solution I containing 1.2mol/L ferric nitrate was prepared, and 85g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 50ml of a solution IV containing 0.62mol/L ammonium molybdate hydrate, 1.96mol/L ammonium metavanadate, 0.3mol/L zinc nitrate and 0.16mol/L antimony nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 70 ℃, and 1mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.1, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 7.8, aging at 85 ℃ for 6 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 430 ℃ in an air atmosphere to obtain the catalyst A3, wherein the weight parts of the components are shown in the table 1.

The catalyst A3 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the pure oxygen is 600h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 1.0, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 200 ℃, the reaction pressure of 1.0MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 4

250Ml of a solution I containing 1.8mol/L ferric nitrate was prepared, and 74g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 20ml of a solution IV containing 1mol/L ammonium metavanadate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 2mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5.4, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 9, aging at 90 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst A4, wherein the weight parts of the components are shown in Table 1.

The catalyst A4 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 780h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.2, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 120 ℃, the reaction pressure of 0.1MPa and the mass space velocity of the hydroxyacetate of 1.0h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 5

200Ml of a solution I containing 2.1mol/L ferric nitrate was prepared, and 75g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 20ml of a solution IV containing 1.4mol/L ammonium metavanadate and 1.5mol/L cobalt nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 7, aging at 90 ℃ for 6 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 600 ℃ in an air atmosphere to obtain the catalyst A5, wherein the weight parts of the components are shown in Table 1.

The catalyst A5 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 780h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.5, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 100 ℃, the reaction pressure of 0.3MPa and the mass space velocity of the hydroxyacetate of 1.0h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 6

100Ml of a solution I containing 0.18mol/L ferric nitrate was prepared, and 94g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. 100ml of a solution IV containing 0.85mol/L cobalt nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 1mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitant III during the period, controlling the pH value of the reaction end point to be 10, aging at 90 ℃ for 6 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 450 ℃ in an air atmosphere to obtain a catalyst A6, wherein the weight parts of the components are shown in Table 1.

The catalyst A6 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume airspeed of the mixed gas of the nitrogen and the pure oxygen is 1000h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 2, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 400 ℃, the reaction pressure of 3.0MPa and the mass airspeed of the hydroxyacetate of 1.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 7

270Ml of a solution I containing 2.6mol/L ferric nitrate was prepared, and 59g of an alumina carrier was added to the solution I with stirring to obtain slurry II. 17ml of a solution IV containing 1mol/L nickel nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 6.2, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 10, aging at 90 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 450 ℃ in an air atmosphere to obtain a catalyst A7, wherein the weight parts of the components are shown in Table 1.

The catalyst A10 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume airspeed of the mixed gas of the nitrogen and the air is 500h ^-1, the molar ratio of oxygen to the hydroxyacetate is 6, the catalyst is contacted and reacted under the conditions of the reaction temperature of 250 ℃, the reaction pressure of 0MPa and the mass airspeed of the hydroxyacetate of 0.3h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in a table 2.

Example 8

150Ml of solution I containing 2.98mol/L ferric nitrate was prepared, and 63g of a silica alumina molecular sieve carrier ZSM-5 was added to the solution I under stirring to obtain slurry II. 100ml of a solution IV containing 0.31mol/L ammonium molybdate hydrate, 0.59mol/L ammonium metavanadate, 0.46mol/L zinc nitrate and 0.51mol/L cobalt nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 110 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitant III during the period, controlling the pH value of the reaction end point to be 10, aging at 120 ℃ for 1 hour, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 150 ℃, and roasting at 600 ℃ in an air atmosphere to obtain a catalyst A8, wherein the weight parts of the components are shown in Table 1.

The catalyst A8 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume airspeed of the mixed gas of the nitrogen and the pure oxygen is 900h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 0.1, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 200 ℃, the reaction pressure of 0MPa and the mass airspeed of the hydroxyacetate of 5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in a table 2.

Example 9

230Ml of solution I containing 1.56mol/L ferric nitrate was prepared, and 77g of a silica alumina molecular sieve carrier ZSM-5 was added to the solution I under stirring to obtain slurry II. 30ml of a solution IV containing 0.7mol/L ammonium molybdate hydrate and 0.6mol/L ammonium metavanadate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 80 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 8.8, aging at 90 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 110 ℃, and roasting at 350 ℃ in an air atmosphere to obtain the catalyst A9, wherein the weight parts of the components are shown in the table 1.

The catalyst A9 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the rich anode is 936h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 2, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 130 ℃, the reaction pressure of 0.1MPa and the mass space velocity of the hydroxyacetate of 1.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 10

200Ml of solution I containing 1.52mol/L ferric nitrate was prepared, and 79g of a carrier ZSM-5 of a silica alumina molecular sieve was added to the solution I under stirring to obtain slurry II. 30ml of a solution IV containing 0.7mol/L ammonium molybdate hydrate and 1.3mol/L ammonium metavanadate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitant III during the period, controlling the pH value of the reaction end point to be 8.3, aging at 90 ℃ for 4 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst A10, wherein the weight parts of the components are shown in Table 1.

The catalyst A10 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 900h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 1.5, the catalyst A is contacted and reacted with the catalyst under the conditions of the reaction temperature of 110 ℃, the reaction pressure of 0.2MPa and the mass space velocity of the hydroxyacetate of 1.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 11

According to the catalyst formulation of example 2, the alumina carrier was replaced with a silica alumina molecular sieve carrier ZSM-5, i.e., 200ml of solution I containing 1.34mol/L ferric nitrate was prepared, and 79.8 silica alumina molecular sieve carrier ZSM-5 was added to the solution I under stirring to obtain slurry II. 30ml of a solution IV containing 0.7mol/L ammonium molybdate hydrate, 1.96mol/L ammonium metavanadate and 0.03mol/L ammonium tungstate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.7, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 8.5, aging at 90 ℃ for 4 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 500 ℃ in an air atmosphere to obtain the catalyst A11, wherein the weight parts of the components are shown in the table 1.

The catalyst A11 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the oxygen-enriched gas is 900h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 1.5, the catalyst A is contacted and reacted with the catalyst under the conditions of the reaction temperature of 120 ℃, the reaction pressure of 0.2MPa and the mass space velocity of the hydroxyacetate of 1.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 12

According to the catalyst formulation of example 4, the alumina carrier was replaced with a silica alumina molecular sieve carrier ZSM-5, namely 250ml of solution I containing 1.8mol/L ferric nitrate was prepared, and 74g of the silica alumina molecular sieve carrier ZSM-5 was added to the solution I under stirring to obtain slurry II. 20ml of a solution IV containing 1mol/L ammonium metavanadate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 2mol/L ammonia water solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5.4, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 9, aging at 100 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst A12, wherein the weight parts of the components are shown in Table 1.

The catalyst A12 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume airspeed of the mixed gas of the nitrogen and the air is 780h ^-1, the molar ratio of oxygen to the hydroxyacetate is 1, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 120 ℃, the reaction pressure of 0.1MPa and the mass airspeed of the hydroxyacetate of 1.0h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in a table 2.

Example 13

According to the catalyst formulation of example 3, the precipitant ammonia solution was replaced with sodium hydroxide solution, i.e., 75ml of solution I containing 1.2mol/L ferric nitrate was prepared, and 85g of alumina carrier was added to the solution I with stirring to obtain slurry II. 50ml of a solution IV containing 0.62mol/L ammonium molybdate hydrate, 1.96mol/L ammonium metavanadate, 0.3mol/L zinc nitrate and 0.16mol/L antimony nitrate was prepared. Under stirring, the temperature of the slurry II is raised to 90 ℃, and 1.25mol/L sodium hydroxide solution is used as a precipitant III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.1, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 7.8, aging at 90 ℃ for 6 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 430 ℃ in an air atmosphere to obtain the catalyst A13, wherein the weight parts of the components are shown in the table 1.

The catalyst A13 is taken in a fixed bed tubular reactor, pure oxygen, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the pure oxygen is 600h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 1.0, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 160 ℃, the reaction pressure of 0.5MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 14

According to the catalyst formulation of example 2, the precipitant ammonia solution was changed to sodium hydroxide solution, i.e., 200ml of solution I containing 1.34mol/L ferric nitrate was prepared, and 79.8g of silica alumina molecular sieve carrier ZSM-5 was added to the solution I with stirring to obtain slurry II. 30ml of a solution IV containing 0.7mol/L ammonium molybdate hydrate, 1.96mol/L ammonium metavanadate and 0.03mol/L ammonium tungstate was prepared. Under stirring, the temperature of the slurry II is raised to 90 ℃, and 3mol/L sodium hydroxide solution is used as a precipitant III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 4.7, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 8.5, aging at 90 ℃ for 4 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 500 ℃ in an air atmosphere to obtain the catalyst A14, wherein the weight parts of the components are shown in the table 1.

The catalyst A14 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 840h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.5, the catalyst is contacted and reacted under the conditions of the reaction temperature of 150 ℃, the reaction pressure of 0.4MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 15

According to the catalyst formulation of example 5, the precipitant ammonia solution was changed to sodium bicarbonate solution, i.e., 200ml of solution I containing 2.1mol/L ferric nitrate was prepared, and 75g of alumina carrier was added to the solution I with stirring to obtain slurry II. 20ml of a solution IV containing 1.4mol/L ammonium metavanadate and 1.5mol/L cobalt nitrate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 3mol/L ammonium bicarbonate solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 7, aging at 90 ℃ for 6 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 100 ℃, and roasting at 600 ℃ in an air atmosphere to obtain the catalyst A15, wherein the weight parts of the components are shown in Table 1.

The catalyst A15 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 780h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.5, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 100 ℃, the reaction pressure of 0.3MPa and the mass space velocity of the hydroxyacetate of 1.0h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Example 16

According to the catalyst formulation of example 9, the precipitant ammonia solution was changed to ammonium bicarbonate solution, namely 250ml of solution I containing 1.8mol/L ferric nitrate was prepared, and 74g of silica alumina molecular sieve carrier ZSM-5 was added to the solution I under stirring to obtain slurry II. 20ml of a solution IV containing 1mol/L ammonium metavanadate was prepared. Under the stirring condition, the temperature of the slurry II is raised to 90 ℃, and 2mol/L ammonium bicarbonate solution is used as a precipitator III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 5.4, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitator III during the period, controlling the pH value of the reaction end point to be 9, aging at 90 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst A16, wherein the weight parts of the components are shown in Table 1.

The catalyst A16 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume airspeed of the mixed gas of the nitrogen and the air is 780h ^-1, the molar ratio of oxygen to the hydroxyacetate is 1, the catalyst is contacted and reacted with the catalyst under the conditions of the reaction temperature of 120 ℃, the reaction pressure of 0.1MPa and the mass airspeed of the hydroxyacetate of 1.0h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in a table 2.

Example 17

200Ml of a solution I containing 3.6mol/L ferric nitrate was prepared, and 40g of an alumina carrier was added to the solution I with stirring to obtain slurry II. 100ml of a solution IV containing 1mol/L ammonium molybdate, 1mol/L ammonium metavanadate and 0.76mol/L zinc nitrate was prepared. Under stirring, the temperature of the slurry II is raised to 90 ℃, and 3mol/L sodium hydroxide solution is used as a precipitant III to be added into the slurry II in a dropwise manner. When the pH value of the slurry is 8, dropwise adding the solution IV into the slurry II, continuously dropwise adding the precipitant III during the period, controlling the pH value of the reaction end point to be 10, aging at 90 ℃ for 3 hours, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 90 ℃, and roasting at 500 ℃ in an air atmosphere to obtain the catalyst A17, wherein the weight parts of the components are shown in Table 1.

The catalyst A17 is taken in a fixed bed tubular reactor, air, nitrogen and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the air is 500h ^-1, the molar ratio of oxygen to the hydroxyacetate is 0.3, the catalyst is contacted and reacted under the conditions of the reaction temperature of 250 ℃, the reaction pressure of 0.2MPa and the mass space velocity of the hydroxyacetate of 0.2h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in Table 2.

Comparative example 1

100Ml of a solution I containing 1.79mol/L ferric nitrate was prepared, and 90g of an alumina carrier was added to the solution I with stirring to obtain a slurry II. Under the stirring condition, raising the temperature of the slurry II to 90 ℃, dropwise adding 1.5mol/L ammonia water solution serving as a precipitator III into the slurry II, controlling the pH value of a reaction end point to be 8.5, aging for 3 hours at 90 ℃, washing the slurry with deionized water, filtering to obtain a filter cake VII, introducing nitrogen into an oven, drying the filter cake VII at 120 ℃, and roasting at 450 ℃ in an air atmosphere to obtain the catalyst D1.

The catalyst D1 is taken in a fixed bed tubular reactor, air and hydroxyacetate are taken as raw materials, wherein the total volume space velocity of air is 840h ^-1, the molar ratio of oxygen to hydroxyacetate is 0.5, the catalyst is contacted and reacted under the conditions of the reaction temperature of 180 ℃, the reaction pressure of 0.6MPa and the mass space velocity of hydroxyacetate of 0.5h ^-1, the gas and the liquid of the reacted product are separated, the liquid phase is sampled and analyzed, and the reaction result is shown in table 1.

Comparative example 2 (C3 is CN107445232B catalyst prepared in example 3)

And (3) taking the catalyst C3 in a fixed bed reactor, taking pure oxygen, nitrogen and hydroxyacetate as raw materials, wherein the total volume space velocity of the mixed gas of the nitrogen and the pure oxygen is 600h ^-1, the molar ratio of the oxygen to the hydroxyacetate is 1.0, carrying out contact reaction with the catalyst under the conditions of the reaction temperature of 160 ℃, the reaction pressure of 0.5MPa and the mass space velocity of the hydroxyacetate of 0.5h ^-1, separating gas from liquid of a product after the reaction, and carrying out sampling analysis on a liquid phase, wherein the reaction result is shown in table 1 (the application condition is the application condition of the embodiment 13).

TABLE 1

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TABLE 2

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The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims

1. An oxidative dehydrogenation catalyst is characterized by comprising an active component, an auxiliary agent and a carrier, wherein the active component is an oxygen-containing compound of iron, and the auxiliary agent is a compound of at least one metal element selected from tungsten, vanadium, cobalt, nickel, molybdenum, zinc and antimony.

2. The oxidative dehydrogenation catalyst of claim 1, further comprising at least one of the following technical characteristics:

a2 According to the weight portions, the iron element in the active component is 1 to 40 portions, the metal element in the auxiliary agent is 1 to 20 portions, and the carrier is 40 to 98 portions.

3. The oxidative dehydrogenation catalyst of claim 2 wherein in a 3) the active component comprises 5 to 25 parts of elemental iron, the promoter comprises 1 to 12 parts of elemental metal, and the support comprises 63 to 94 parts.

4. A process for preparing an oxidative dehydrogenation catalyst according to any one of claims 1 to 3 comprising the steps of:

1) Adding a precipitant solution into the first slurry containing the salt of the iron element in the active component and the carrier until the pH value of the mixed solution is 4-8, and adding a soluble salt solution containing the metal element in the auxiliary agent until the precipitation reaction is ended to obtain a second slurry;

2) Aging and filtering the second slurry to obtain a filter cake;

5. The method of manufacturing of claim 4, further comprising at least one of the following features:

11 In step 1), the precipitant is at least one selected from alkali metal bicarbonate, hydroxide and ammonia water;

12 In step 1), the pH value of the end point of the precipitation reaction is 7-10;

13 In step 1), the temperature of the precipitation reaction is 70-110 ℃;

21 In step 2), the aging temperature is 85-120 ℃;

22 In step 2), the aging time is 1 to 12 hours;

31 In step 3), drying is carried out under the nitrogen atmosphere;

32 In step 3), the drying temperature is 90-150 ℃;

33 In step 3), roasting is carried out under an air atmosphere;

34 In step 3), the roasting temperature is 350-600 ℃.

6. Use of an oxidative dehydrogenation catalyst according to any of claims 1 to 3 for the oxidative dehydrogenation of glycolate esters with an oxygen molecule-containing gas to obtain aldehyde acetate esters.

7. The use of the oxidative dehydrogenation catalyst according to claim 6, further comprising at least one of the following technical characteristics:

b1 In a fixed bed tubular reactor;

b2 Oxygen molecules from pure oxygen or air;

b4 The mass airspeed of the hydroxyacetate is 0.2-5 h ^-1;

b5 The gas airspeed of the oxygen-containing molecules is 500-1000 h ^-1;

b6 Molar ratio of oxygen molecules to glycolate in the oxygen molecule-containing gas is (0.1 to 6): 1, a step of;

b7 The pressure of the oxidative dehydrogenation reaction is 0-3 Mpa;

b8 The temperature of the oxidative dehydrogenation reaction is 100-400 ℃.

8. A process for the oxidative dehydrogenation of a hydroxyacetate to form an aldoacetate, wherein the hydroxyacetate is reacted with a molecular oxygen-containing gas in the presence of an oxidative dehydrogenation catalyst according to any one of claims 1 to 3 to form the aldoacetate.

9. The method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate according to claim 8, further comprising at least one of the following technical features:

c1 In a fixed bed tubular reactor;

c2 Oxygen molecules from pure oxygen or air;

c4 The mass airspeed of the hydroxyacetate is 0.2-5 h ^-1;

c5 The gas airspeed of the oxygen-containing molecules is 500-1000 h ^-1;

c6 Molar ratio of oxygen molecules to glycolate in the oxygen molecule-containing gas is (0.1 to 6): 1, a step of;

c7 The pressure of the oxidative dehydrogenation reaction is 0-3 Mpa;

c8 The temperature of the oxidative dehydrogenation reaction is 100-400 ℃.

10. The method for synthesizing aldehyde acetate by oxidative dehydrogenation of hydroxyacetate according to claim 9, further comprising at least one of the following technical features: