CN115739177A - Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate - Google Patents

Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate Download PDF

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CN115739177A
CN115739177A CN202211571974.6A CN202211571974A CN115739177A CN 115739177 A CN115739177 A CN 115739177A CN 202211571974 A CN202211571974 A CN 202211571974A CN 115739177 A CN115739177 A CN 115739177A
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potassium
carrier
oxygen
precursor
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CN115739177B (en
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杨志超
李光
王雷雷
许庆峰
孔德彬
卜令军
孙康
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses an acetyl oxidation catalyst, a preparation method thereof and a method for preparing vinyl acetate, wherein the catalyst comprises a carrier, an additive, an active component and an auxiliary agent; the main chemical component of the carrier is SiO 2 、Al 2 O 3 、Fe 2 O 3 Or mixtures thereof; the additive is an indigoid compound or a derivative thereof; the active component comprises (a) Pd element and (b) at least one of Cu, au and Sn; the aidThe agent is potassium polycarboxylate. The invention mainly solves the problems of low activity and selectivity of the catalyst in the prior art, and can be industrially applied to C 2 ‑C 4 Alkene, acetic acid and oxygen are subjected to acetyl oxidation reaction to prepare the vinyl acetate.

Description

Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to an acetyl oxidation catalyst, a preparation method thereof and a method for preparing vinyl acetate.
Background
Vinyl acetate is an important organic synthesis intermediate, and typical vinyl acetate is vinyl acetate, allyl acetate, methyl allyl alcohol acetate and the like. The allyl acetate is a colorless inflammable liquid, is slightly soluble in water, is easily soluble in alcohol and ether, can be dissolved in acetone, is used as an important chemical raw material, is mainly used for producing important organic synthetic raw materials such as allyl alcohol, epoxy chloropropane, glycerol and the like, and is also used for synthesizing resin and an adhesive.
In the 80 s of the 20 th century, japanese Showa electrician first realized the industrial production of allyl acetate, showa electrician developed acetyl oxidation technology, and in the presence of palladium and a cocatalyst, propylene, oxygen and acetic acid are used as raw materials, a fixed bed gas phase reaction is adopted to prepare allyl acetate, and SiO is used as an acetyl oxidation catalyst 2 、Al 2 O 3 Or SiO 2 And Al 2 O 3 The formed mixture is a carrier, palladium, copper and potassium acetate are loaded, and the palladium and copper active components are distributed in an eggshell shape.
Patent publication No. CN 104107722B describes an allyl acetate catalyst, which is prepared by adding a nitrogen oxide compound as an auxiliary agent to solve the problem of low activity and selectivity of the catalyst, wherein the auxiliary agent solves the problem of low activity and selectivity of the catalyst, but the auxiliary agent is lost and difficult to supplement in industrial production, so that the service life of the catalyst in industry is limited.
Patent publication No. CN 1131199C describes an oxyacylation catalyst for the preparation of allyl acetate, which catalyst is added with metallic tin or a mixture of tin and an additional promoter metal during the preparation process, and by adding tin, the catalyst life can be maintained without deterioration without adding water to the raw materials. Since water is produced in the acetoxylation reaction and the produced water removes a part of the heat generated in the acetoxylation reaction, the method by which water is not added has no industrial advantage.
Patent publication No. CN 103120961B describes an allyl acetate catalyst and a preparation method thereof. The catalyst is made of SiO 2 、Al 2 O 3 Or the mixture thereof is used as a carrier, the loaded active component comprises metal palladium, metal copper and alkali metal acetate, and the average grain diameter of palladium copper crystal grains is 5-7nm; in the preparation process of the catalyst, liquid carbon dioxide is used as an impregnation liquid, the used palladium compound is acetylacetone group as a ligand, and the preparation method adopts expensive raw materials, so that the production cost is too high, and the industrial application economy is not achieved.
The patent with publication number CN 104437622B describes an allyl acetate catalyst and a preparation method thereof, wherein a carrier of the catalyst comprises a carrier, an active component and a cocatalyst, the carrier is treated by ultrasonic waves in the presence of organic amine in the preparation process to prepare the catalyst, the organic amine adopted in the preparation method is expensive, the ultrasonic wave treatment is not beneficial to industrial scale-up production, and the catalyst is not beneficial to industrial large-scale application.
Therefore, there is a need to develop a catalyst having high activity and good industrial application prospects.
Disclosure of Invention
The invention aims to provide a catalyst for acetyl oxidation and a preparation method thereof, wherein the acetyl oxidation catalyst is added with an indigoid compound or a derivative thereof, so that the dispersibility of active components is better, and the activity and the selectivity of the catalyst are higher; the indigoid compound or the derivative thereof can interact with the auxiliary agent potassium polycarboxylic acid, reduce the loss of the auxiliary agent potassium ions, maintain the activity and the selectivity of the catalyst and prolong the service life of the catalyst.
The invention also aims to provide a method for preparing an allyl acetate compound, in particular to a method for preparing an allyl acetate compound, which has the characteristics of high activity and high selectivity when used for preparing allyl acetate under the action of the catalyst provided by the invention.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an acetyl oxidation catalyst comprising a support, an additive, an active component, and an adjunct;
the main chemical component of the carrier is SiO 2 、Al 2 O 3 、Fe 2 O 3 Or a mixture thereof;
the additive is at least one of an indigoid compound or a derivative thereof;
the active component comprises (a) Pd element and (b) at least one of Cu, au and Sn;
the auxiliary agent is potassium polycarboxylate.
Preferably, the specific surface area of the carrier is 100 to 600m 2 The volume of pores is 0.3-1.2mL/g, the average pore diameter is 5-20nm, and the bulk density is 300-900g/L.
Further, the specific surface area of the carrier is 120-400m 2 Per g, more preferably from 150 to 300m 2 (ii)/g; the pore volume is 0.4-1.0mL/g, more preferably 0.6-0.9mL/g; an average pore diameter of 6 to 19nm, more preferably 9 to 18nm; the bulk density is 350 to 800g/L, more preferably 400 to 700g/L.
Preferably, the content of the indigoid compound or the derivative thereof is 0.05-10g/L, preferably 0.2-8g/L, and more preferably 0.5-6g/L; the indigo compound or its derivative is at least one selected from indigo, isoindigo, isatin, indirubin, methyl isatin, hydroxyl isatin, allyl isatin, benzyl isatin, thioindigo and thioisatin.
The active component comprises a component (a) and a component (b), wherein the component (a) is palladium, and the component (b) is at least one of copper, gold and tin, preferably, the content of the palladium (a) in the active component is 0.5-15g/L, more preferably 0.6-10g/L; the content of (b) in the active ingredient is 0.1 to 10g/L, more preferably 0.2 to 6g/L.
The auxiliary agent is potassium polycarboxylate, preferably, the potassium polycarboxylate is at least one of potassium tartrate, potassium malate, potassium oxalate and potassium citrate, and more preferably, the potassium citrate and the potassium tartrate; the content of the potassium polycarboxylate is 5-80g/L, and more preferably 10-70g/L.
The preparation method of the catalyst comprises the following steps:
1) Roasting a carrier: roasting the carrier at a certain temperature by taking oxygen-containing gas as carrier gas to obtain a treated carrier;
2) Loading an additive: preparing a solution containing an indigoid compound or a derivative thereof, slowly adding the prepared additive solution into the carrier obtained in the step 1), aging for a period of time, and then drying at a certain temperature to obtain a catalyst precursor 1;
3) Active component loading and fixing: preparing a salt solution containing active component elements, slowly adding the prepared active component solution into the precursor 1 obtained in the step 2), and then putting the catalyst precursor 1 impregnated with the active components into alkali liquor for active component fixation to obtain a catalyst precursor 2;
4) Reduction of active components: reacting the catalyst precursor 2 obtained in the step 3) with a reducing agent for reduction treatment, washing and drying to obtain a catalyst precursor 3;
5) Addition of an auxiliary agent: and preparing a certain amount of potassium polycarboxylate solution, soaking the solution into the catalyst precursor 3, and drying to obtain a catalyst finished product.
Further, the oxygen-containing carrier gas in the step 1) is at least one of air, oxygen and a mixture of oxygen and nitrogen, preferably air; the calcination temperature is 300-900 ℃, preferably 350-750 ℃.
Further, in the step 2, the aging time is 0.5-6h, and the drying temperature is 100-300 ℃.
The inventor researches and discovers that the addition of the indigoid compound or the derivative thereof influences the dispersion of palladium and other metal elements in the active component, and compared with a catalyst prepared without adding the indigoid compound or the derivative thereof, the addition of a proper amount of the indigoid compound or the derivative thereof can obviously promote the dispersion of the active component, the dispersion degree of the active component is higher, more palladium active sites are exposed, raw materials participating in the reaction are easier to be activated, and the activity and the selectivity of the catalyst are higher.
Further, in step 3, the palladium salt is at least one of sodium chloropalladate, potassium chloropalladate, palladium chloride, palladium acetate, palladium nitrate and palladium sulfate, preferably sodium chloropalladate and palladium chloride; the salt containing the element (b) is at least one of soluble chloride, nitrate, acetate, sulfide and the like of copper, gold and tin, and preferably soluble chloride; the alkali liquor is at least one of water solutions of sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, preferably the water solution of sodium silicate and/or sodium hydroxide, and the amount of the alkali liquor is enough to completely precipitate the free active components (a) and (b).
Further, in the step 4, the reducing agent includes at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene and isobutylene, preferably hydrazine hydrate and hydrogen. The reducing agent is used in an amount that enables complete reduction of the active components (a) and (b) in the oxidation state.
The inventor finds that the potassium polycarboxylate is more favorable for improving the activity of the oxygen acylation reaction and inhibiting the side reaction of generating carbon dioxide compared with the potassium monocarboxylate, and improves the catalytic activity and the selectivity of a target product; and the potassium polycarboxylate can form interaction with the indigoid compound or derivatives thereof, the auxiliary agent potassium ions are not easy to lose, the activity and selectivity of the catalyst can be maintained, and the service life of the catalyst is long.
The method for preparing vinyl acetate comprises the steps of using acetic acid, oxygen and C in the presence of the catalyst 2 -C 4 Olefin is used as a raw material, and the vinyl acetate is prepared through acetyl oxidation reaction.
Further, the method for preparing the vinyl acetate comprises the following steps:
mixing acetic acid, oxygen and C 2 -C 4 The olefin feed is fed to a reactor packed with the catalyst of the invention in terms of molar ratio, C 2 -C 4 Olefin, acetic acid, oxygen =1, (0.1-0.5), acetyl oxidation reaction is carried out at 120-180 ℃ and 0.1-1.5MPaG, and volume space velocity is 1000-3000h -1 To prepare vinyl acetate;
preferably, said C 2 -C 4 The olefin raw material is propylene;
further, a process for producing allyl acetateThe molar ratio of the materials is that propylene, acetic acid, oxygen and water are =1 (0.1-0.5) to (0.1-1), the acetyloxidation reaction is carried out at 120-180 ℃ and 0.1-1.5MPaG, and the volume space velocity is 1000-3000h -1 And allyl acetate is prepared.
The invention has the following beneficial effects:
1) The acetyl oxidation catalyst is added with an indigoid compound or a derivative thereof, so that the active component has better dispersibility and higher catalytic activity and selectivity, and the problem that the catalyst for synthesizing vinyl acetate in the prior art has low activity and selectivity is solved.
2) The catalyst auxiliary agent adopts potassium polycarboxylate, so that compared with potassium monocarboxylate, the catalyst auxiliary agent is more favorable for improving the activity of oxygen acylation reaction and inhibiting the side reaction of generating carbon dioxide, and the catalytic activity and the selectivity of a target product are improved; and the potassium polycarboxylate can form interaction with the indigoid compound or derivatives thereof, the auxiliary agent potassium ions are not easy to lose, the activity and selectivity of the catalyst are maintained, and the service life of the catalyst is long.
3) Compared with the prior catalyst preparation technology, the acetyl oxidation catalyst provided by the invention has the advantages of simple steps, low raw material cost, production cost saving and industrial application competitiveness.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The calculation methods and test methods used in the examples or comparative examples are as follows:
1. the contents of the components in the reaction product were analyzed by gas chromatography using an Agilent GC 8890A chromatograph, and the activity and selectivity of the catalyst were calculated according to the following formulas
Figure BDA0003988045000000061
2. Method for measuring information of specific surface area and pore structure of catalyst
Pore structure of catalyst by N 2 The specific surface area is measured by a physical adsorption method, the specific surface area is obtained by a BET method and the pore volume is obtained by a BJH desorption method, and the model of a testing instrument is Micromeritics ASAP 2460.
3. Determination of particle size of catalyst active component
A certain amount of the catalyst was pulverized with a mortar to obtain a uniform powder, and then the catalyst powder was ultrasonically dispersed in absolute ethanol, as measured by a JEOL 2100plus Transmission Electron Microscope (TEM).
4. Analysis of loss of catalyst promoter elements
A certain amount of the sample produced by the reaction was taken, and the potassium element contained in the sample was measured by a Seimer FeiCAP PRO type inductively coupled plasma spectrometer (ICP).
[ example 1 ] A method for producing a polycarbonate
1) Preparation of the catalyst
Taking 1L of silica gel beads (average particle diameter of 5mm, specific surface area of 221 m) 2 The pore volume is 0.86mL/g, the average pore diameter is 14.5nm, and the bulk density is 504 g/L), and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ in an air atmosphere;
preparing 296mL of aqueous solution containing 2.1g of indigo, fully and uniformly stirring, uniformly spraying and moistening the aqueous solution on the silica gel pellets, standing for 4 hours, and then completely drying in an oven at 150 ℃;
preparing 420mL of aqueous solution containing 4.8g of Pd and 1.0g of Cu, sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel balls, preparing 1.2L of solution containing 53.5g of sodium nonahydrate, and putting the silica gel balls into the sodium silicate solution to obtain a catalyst precursor A;
then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, and drying in a drying oven to obtain a catalyst precursor B;
the prepared 400mL solution containing 55g of potassium citrate was impregnated onto catalyst precursor B and dried thoroughly to obtain the final catalyst. The average particle size of the active ingredient was 3.2nm by analysis.
2) Testing of catalyst Performance
Putting 500mL of catalyst into a fixed bed reactor with the inner diameter of 3cm and the height of 150cm, filling inert ceramic balls at the upper end and the lower end of the catalyst, testing leakage by using nitrogen, heating a reaction system, introducing reaction raw materials, controlling the reaction temperature to be 145 ℃, the reaction pressure to be 0.75MPaG, and the volume space velocity to be 2000h -1 The composition of the raw materials was propylene, acetic acid, oxygen, water =1, 0.25, and after a stable reaction for 100 hours, the mixture obtained by the above reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the initial activity of the catalyst is 436 g/L.h, and the selectivity of allyl acetate is 96.8%; after the continuous evaluation for 3000h, through analysis, no potassium ion is detected in the reaction solution, the catalyst activity is 373 g/L.h, the allyl acetate selectivity is 96.3%, and the catalyst activity and selectivity can still meet the industrial use requirements.
[ example 2 ]
1) Preparation of the catalyst
Taking 1L of silica gel beads (average particle diameter of 5.5mm, specific surface area of 168 m) 2 The pore volume is 0.73mL/g, the average pore diameter is 16.3nm, and the bulk density is 522 g/L), and the mixture is put into a muffle furnace to be roasted for 2 hours at 700 ℃ in an air atmosphere;
preparing 320mL of aqueous solution containing 0.5g of thioindigo red, fully and uniformly stirring, uniformly spraying and moistening the aqueous solution on the silica gel pellets, standing for 4 hours, and then completely drying in an oven at 200 ℃;
preparing 420mL of aqueous solution containing 6.0g of Pd and 0.6g of Cu, sodium chloropalladate and copper acetate, fully and uniformly stirring, adding the aqueous solution into the silica gel beads, preparing 1.2L of solution containing 46g of sodium nonahydrate, and putting the silica gel beads into the sodium silicate solution to obtain a catalyst precursor A;
and then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, drying in an oven to obtain a catalyst precursor B, soaking the catalyst precursor B in 400mL of solution containing 60g of potassium tartrate, and fully drying to obtain a catalyst finished product. The average particle size of the active ingredient was 3.0nm by analysis.
2) Testing of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and after stable reaction for 100 hours, the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. The analysis shows that the activity of the catalyst is 424g/L/h, and the selectivity of allyl acetate is 96.1%. After the continuous evaluation for 3000 hours, through analysis, no potassium ion is detected in the reaction liquid, the catalyst activity is 348g/L/h, the allyl acetate selectivity is 95.6%, and the catalyst activity and selectivity can still meet the industrial use requirements.
[ example 3 ]
1) Preparation of the catalyst
Taking 1L silica gel pellet (average particle diameter 5mm, specific surface area 289 m) 2 The pore volume is 0.92mL/g, the average pore diameter is 12.4nm, the bulk density is 476 g/L), and the mixture is put into a muffle furnace to be roasted for 8 hours at 350 ℃ in an air atmosphere;
preparing 365mL of aqueous solution containing 3.2g of indirubin, fully and uniformly stirring, uniformly spraying and moistening the aqueous solution on the silica gel pellets, standing for 8 hours, and then completely drying in a drying oven at 110 ℃;
preparing 420mL of aqueous solution of sodium chloropalladate and copper chloride containing 4.5g of Pd and 0.8g of Cu, fully and uniformly stirring, adding the aqueous solution into the silica gel beads, preparing 1.2L of solution containing 19g of sodium nonahydrate, and putting the silica gel beads into the sodium silicate solution to obtain a catalyst precursor A; and then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, drying in an oven to obtain a catalyst precursor B, soaking the prepared 400mL of solution containing 60g of potassium malate on the catalyst precursor B, and fully drying to obtain a catalyst finished product. The average particle size of the active ingredient was 3.6nm by analysis.
2) Testing of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and after stable reaction for 100 hours, the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the activity of the catalyst is 418g/L/h, and the selectivity of allyl acetate is 96.6%. After the continuous evaluation for 3000 hours, through analysis, no potassium ion is detected in the reaction liquid, the catalyst activity is 341g/L/h, the allyl acetate selectivity is 96.0%, and the catalyst activity and selectivity can still meet the industrial use requirements.
Comparative example 1
1) Preparation of the catalyst
The indigo compound or the derivative thereof is not used as an additive on the surface of the carrier in the preparation process of the catalyst.
Taking 1L of silica gel beads (average particle diameter of 5mm, specific surface area of 221 m) 2 The pore volume is 0.86mL/g, the average pore diameter is 14nm, and the bulk density is 504 g/L), and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ in an air atmosphere;
preparing 420mL of aqueous solution containing 4.8g of Pd and 1.0g of Cu, sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel balls, preparing 1.2L of solution containing 53.5g of sodium nonahydrate, and putting the silica gel balls into the sodium silicate solution to obtain a catalyst precursor A; and then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, drying in an oven to obtain a catalyst precursor B, soaking the catalyst precursor B in 400mL of solution containing 55g of potassium citrate, and fully drying to obtain a catalyst finished product. The average particle size of the active ingredient was 5.2nm by analysis.
The catalyst evaluation conditions were the same as in example 1, and after stable reaction for 100 hours, the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the catalyst activity is 382g/L/h, and the allyl acetate selectivity is 94.2%. After the continuous evaluation for 3000 hours, through analysis, the potassium ion content in the reaction liquid is 6.2ppm, potassium loss exists, the catalyst activity is 283g/L/h, the allyl acetate selectivity is 90.4%, and the catalyst activity and selectivity can not meet the industrial use requirements.
Comparative example 2
1) Preparation of the catalyst
In the preparation process of the catalyst, the surface of the carrier does not adopt a potassium polycarboxylate auxiliary agent, and adopts a conventional potassium acetate auxiliary agent.
Taking 1L silica gel pellet (average particle size 5 m)m, specific surface area 221m 2 The pore volume is 0.86mL/g, the average pore diameter is 14nm, and the bulk density is 504 g/L), and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ in an air atmosphere;
preparing 296mL of aqueous solution containing 2.1g of indigo, fully and uniformly stirring, uniformly spraying and moistening the aqueous solution on the silica gel pellets, standing for 4 hours, and then completely drying in an oven at 150 ℃;
preparing 420mL of aqueous solution containing 4.8g of Pd and 1.0g of Cu, sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel balls, preparing 1.2L of solution containing 53.5g of sodium nonahydrate, and putting the silica gel balls into the sodium silicate solution to obtain a catalyst precursor A; and then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, drying in an oven to obtain a catalyst precursor B, soaking the catalyst precursor B in 400mL of solution containing 55g of potassium acetate, and fully drying to obtain a catalyst finished product. The average particle size of the active ingredient was 3.5nm by analysis.
The catalyst evaluation conditions were the same as in example 1, and after stable reaction for 100 hours, the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the catalyst activity is 412g/L/h, and the allyl acetate selectivity is 95.0%. After the continuous evaluation for 3000 hours, through analysis, the potassium ion content in the reaction liquid is 10.5ppm, potassium loss exists, the catalyst activity is 262g/L/h, the allyl acetate selectivity is 88.6%, and the catalyst activity and selectivity can not meet the industrial use requirements.
Comparative example 3
1) Preparation of the catalyst
In the preparation process of the catalyst, the surface of the carrier does not adopt additives such as indigoid compounds or derivatives thereof and polycarboxylic acid potassium auxiliary agents.
Taking 1L of silica gel beads (average particle diameter of 5mm, specific surface area of 221 m) 2 The pore volume is 0.86mL/g, the average pore diameter is 14nm, and the bulk density is 504 g/L), and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ in an air atmosphere; 420mL of an aqueous solution of sodium chloropalladate and copper chloride containing 4.8g of Pd and 1.0g of Cu was prepared, and the mixture was sufficiently stirredUniformly mixing, adding the mixture into the silica gel balls to prepare 1.2L of solution containing 53.5g of sodium silicate nonahydrate, and putting the silica gel balls into the sodium silicate solution to obtain a catalyst precursor A; and then adding 40g of 80% hydrazine hydrate solution into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ion is detected, drying in an oven to obtain a catalyst precursor B, soaking the catalyst precursor B in 400mL of solution containing 55g of potassium acetate, and fully drying to obtain a catalyst finished product. The average particle size of the active ingredient was 6.1nm by analysis.
The catalyst evaluation conditions were the same as in example 1, and after stable reaction for 100 hours, the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. The catalyst activity is 352g/L/h and the allyl acetate selectivity is 94.3 percent by analysis. After the continuous evaluation for 3000 hours, through analysis, the potassium ion content in the reaction liquid is 15.4ppm, potassium loss exists, the catalyst activity is 227g/L/h, the allyl acetate selectivity is 84.1%, and the catalyst activity and selectivity can not meet the industrial use requirements.
From the above test results it can be seen that:
(1) As can be seen from example 1 and comparative example 1, the additive indigo is used in the preparation of the catalyst of example 1, the indigo compound or its derivative is not used in the preparation of the catalyst of comparative example 1, the active size of the catalyst of comparative example 1 is significantly large, and potassium loss is significant, and the initial and long-term activity and selectivity are significantly lower than those of the catalyst of example 1;
(2) As can be seen from the results of example 1 and comparative example 2, the potassium polycarboxylic acid assistant is not adopted in the comparative example 2, the loss of the potassium polycarboxylic acid assistant is obvious in the long-term use process, and the long-term activity and selectivity of the catalyst in the comparative example 2 are obviously lower than those of the catalyst in the example 1;
(3) As can be seen from comparison of example 1 with comparative example 3, without addition of the indigoid compound or its derivative and potassium polycarboxylate, the initial and long-term activity and selectivity of the catalyst of comparative example 3 are significantly lower than those of example 1, and the scheme of the present invention shows higher and longer-lasting catalyst activity and selectivity.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.

Claims (10)

1. An acetyl oxidation catalyst, characterized in that the catalyst comprises a carrier, an additive, an active component and an auxiliary agent;
the additive is at least one of an indigoid compound or a derivative thereof;
the active component comprises (a) Pd element and (b) at least one of Cu, au and Sn;
the auxiliary agent is potassium polycarboxylate.
2. The catalyst of claim 1 wherein the support has a chemical composition of SiO as the major component 2 、Al 2 O 3 、Fe 2 O 3 Or mixtures thereof; preferably, the specific surface area of the carrier is 100 to 600m 2 The volume of pores is 0.3-1.2mL/g, the average pore diameter is 5-20nm, and the bulk density is 300-900g/L.
3. The catalyst according to claim 1 or 2, wherein the indigoid compound or its derivative is at least one selected from the group consisting of indigo, isoindigo, isatin, indirubin, methyl isatin, hydroxyisatin, allyl isatin, benzyl isatin, thioindigo, thioisatin;
preferably, the content of the indigoid compound or the derivative thereof is 0.05-10g/L.
4. The catalyst according to any one of claims 1 to 3, wherein the Pd is contained in an amount of 0.5 to 15g/L and the (b) element is contained in an amount of 0.1 to 10g/L.
5. The catalyst according to any one of claims 1 to 4, wherein the potassium polycarboxylate is at least one of potassium tartrate, potassium malate, potassium oxalate and potassium citrate, preferably the potassium polycarboxylate is present in an amount of 5 to 80g/L.
6. The method for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
1) Roasting a carrier: roasting the carrier at a certain temperature by taking oxygen-containing gas as carrier gas to obtain a treated carrier;
2) Loading an additive: slowly adding a solution of an indigoid compound or a derivative thereof into the carrier obtained in the step 1), aging for a period of time, and then drying at a certain temperature to obtain a catalyst precursor 1;
3) Active component loading and fixing: slowly adding a salt solution containing active component elements into the precursor 1 obtained in the step 2), and then putting the catalyst precursor 1 impregnated with the active components into an alkali liquor to fix the active components to obtain a catalyst precursor 2;
4) Reduction of active components: reacting the catalyst precursor 2 obtained in the step 3) with a reducing agent for reduction treatment, washing and drying to obtain a catalyst precursor 3;
5) Addition of an auxiliary agent: and (3) soaking the potassium polycarboxylate into the catalyst precursor 3, and drying to obtain a catalyst finished product.
7. The method according to claim 6, wherein in step 1), the oxygen-containing carrier gas is at least one of air, oxygen, and a mixture of oxygen and nitrogen; the roasting temperature is 300-900 ℃; and/or:
the drying temperature in the step 2) is 100-300 ℃.
8. The method according to any one of claims 6 to 7, wherein the alkali solution in step 3) is at least one of an aqueous solution of sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide; and/or:
the reducing agent in the step 4) comprises at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene and isobutene.
9. A process for the preparation of an alkenyl acetate, characterized in that acetic acid, oxygen, C are added in the presence of a catalyst according to any one of claims 1 to 5 or prepared according to any one of claims 6 to 8 2 -C 4 Alkene reaction to prepare vinyl acetate.
10. The process for preparing an alkenyl acetate according to claim 9, wherein the reaction temperature is 120 to 180 ℃ and the reaction pressure is 0.1 to 1.5MPaG,
in terms of mole ratio, C 2 -C 4 Olefin, acetic acid, oxygen =1 (0.1-0.5) and (0.1-0.5), the volume space velocity of the raw material is 1000-3000h -1 。
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