CN113649082A - Method for preparing vinyl acetate catalyst by acetylene method - Google Patents

Method for preparing vinyl acetate catalyst by acetylene method Download PDF

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CN113649082A
CN113649082A CN202110930543.3A CN202110930543A CN113649082A CN 113649082 A CN113649082 A CN 113649082A CN 202110930543 A CN202110930543 A CN 202110930543A CN 113649082 A CN113649082 A CN 113649082A
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activated carbon
catalyst
vinyl acetate
acetylene
drying
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冯良荣
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Chengdu Zhongke Purui Purification Equipment Co ltd
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Chengdu Zhongke Purui Purification Equipment Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a method for preparing a vinyl acetate catalyst by using an acetylene method, which is used for preparing the catalyst for synthesizing vinyl acetate by using acetylene and acetic acid as main raw materials. The obtained catalyst has high activity and long service life.

Description

Method for preparing vinyl acetate catalyst by acetylene method
Technical Field
The invention relates to the technical field of catalytic chemistry and synthesis of basic organic chemicals, in particular to a preparation method of a catalyst for synthesizing vinyl acetate by taking acetylene and acetic acid as main raw materials.
Background
Vinyl acetate is also called vinyl acetate, called VAc for short, is an important organic chemical raw material and is one of 50 chemical products with the largest world yield. At present, the technology for producing vinyl acetate mainly comprises an ethylene gas phase method and an acetylene gas phase method. In areas with rich calcium carbide resources, natural gas resources and water and electricity resources, particularly areas with preferential water and electricity during flood peak, the acetylene gas phase method has strong competitiveness due to the advantages of sufficient raw materials and energy, low cost and the like; especially, at the present day that the price of petroleum is soaring, the research of acetylene gas phase method high-efficiency catalyst has a very important meaning.
In 1922, Wacker Germany firstly used a method for synthesizing VAc from acetylene in a gas phase, and then the VAc was put into industrial production through the improvement of Hochst company. The catalyst uses zinc acetate as an active component and active carbon as a carrier, and is used up to now. However, this catalyst has many disadvantages, and in particular, the activity decreases more rapidly. In order to improve the activity of the catalyst and to prolong the service life thereof, researchers have conducted a great deal of research on the active components of the catalyst, the catalyst support and the deactivation of the catalyst.
During the research and industrial production and application of acetylene method vinyl acetate catalyst for years, the inventor finds that one reason for the inactivation and the increase of side reactions of the catalyst is that the main active component zinc acetate of the catalyst is loaded excessively, and although the activity of the catalyst can be increased, the excessive loading causes the active component to migrate from the inner surface to the outer surface of the active carbon particles during the preparation and use of the catalyst and further fall off from the outer surface of the active carbon particles, and the active component is aggregated at the lower part of the catalyst bed layer, so that the synthesis reaction of vinyl acetate at the aggregation part is violent, the byproducts are increased, and part of vinyl acetate is polymerized to further block a reaction tube. The present inventors have therefore proposed a method for preparing a catalyst which not only increases the loading of the main active component of the catalyst, but also prevents the loss of the active component as much as possible, see chinese patents CN103447083A and CN103111325B, and partially solve this problem. However, in the technical solution of the above-mentioned chinese patent, the drying process is performed in a tower-type drying tower, the cross section through which the current flows in the drying tower is relatively large, and the activated carbon particles are not stirred or turned over during the drying process, and the resistivity of the activated carbon or catalyst material pile is continuously reduced along with the evaporation of the moisture, so that the activated carbon at different positions inside the drying tower is heated unevenly. Eventually, part of the catalyst is overheated, so that the catalyst activity is reduced or even deactivated. In addition, if the impregnation process is also completed in the drying tower, a long-time draining process is needed, otherwise the liquid loading of the activated carbon at the lower part of the drying tower is too much, a large amount of zinc acetate crystal grains are still attached to the outer surfaces of the activated carbon particles of the part of the catalyst after drying, and the catalyst is difficult to discharge from the drying tower. However, in the long-time draining process, the temperature of the catalyst material pile in the drying tower is reduced, and zinc acetate in the solution in the inner hole of the active carbon is crystallized and separated out, so that the activity of the catalyst is reduced, and active components are more easily lost and block the lower part of the reaction tube. In fact, once the temperature of the catalyst pile drops after impregnation and before drying or a large amount of zinc acetate crystals are separated out due to other reasons, the prepared catalyst needs to be added with a screening process to screen out the crystallized zinc acetate crystal grains (see Chinese patent CN111203286A, which adds a vibrating screen for screening after the catalyst drying process), and the service life of the catalyst can be reduced by as much as 40%.
Disclosure of Invention
The invention provides a method for preparing a vinyl acetate catalyst by an acetylene method, which aims to solve the technical problems that: in the prior art, zinc acetate is easy to crystallize in inner holes and outer surfaces of active carbon particles, so that the loading capacity of active carbon on active component zinc acetate is reduced, and the catalyst efficiency is influenced.
In view of the above problems of the prior art, according to one aspect of the present disclosure, the following technical solutions are adopted in the present invention:
a method for preparing a vinyl acetate catalyst by an acetylene method comprises the following steps:
step i) impregnation Process
Preparing a zinc salt and/or a cocatalyst component into a solution, then impregnating an activated carbon carrier with the solution, and impregnating the zinc salt and the cocatalyst component on the activated carbon;
step ii) drying process
Heating and drying the impregnated activated carbon to obtain the acetylene method vinyl acetate catalyst;
wherein, the impregnation process of the step i) and the drying process of the step ii) are completed in the same device;
the drying process of the step ii) is to feed current into the impregnated activated carbon, so that the activated carbon generates heat to complete the drying, and the activated carbon is stir-fried in the process.
In order to better realize the invention, the further technical scheme is as follows:
further, the impregnation process of step i) and the drying process of step ii) are performed in a rotary kiln.
Further, in step ii):
the method of feeding current into the impregnated activated carbon is to feed direct or alternating current into the activated carbon by directly connecting the electrodes of the power supply to the impregnated activated carbon, thereby heating the activated carbon.
Further, in step ii):
the method of feeding current to the impregnated activated carbon is by means of alternating current induction.
Further, the activated carbon support is subjected to a plurality of impregnation processes and a plurality of drying processes.
Further, the acid groups of the zinc salt solution used in the multiple impregnation processes are the same or different.
Further, the maximum temperature to which the activated carbon is passed during the last drying process is 200 ℃ or less, and the maximum temperature to which the activated carbon is passed during the remaining drying processes is higher than the decomposition temperature of the zinc salt during the previous impregnation process.
Further, in the drying process, the evaporated gas-phase material is taken out of the device by introducing reaction inert gas or vacuum suction.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a method for preparing a vinyl acetate catalyst by an acetylene method, which comprises the following steps:
1) the activated carbon is heated by directly electrifying the impregnated activated carbon particle pile. Because the active carbon generates heat, the drying speed is high, and the production period of the catalyst is short.
2) Because the activated carbon particles generate heat, the water in the solution is evaporated on the inner surface and the outer surface of the activated carbon particles at the same time, so that the phenomenon that the water is mainly evaporated on the outer surfaces of the activated carbon particles when the activated carbon particles are heated externally is avoided, and the water in the inner holes of the particles brings active components in the inner holes to the outer surfaces of the activated carbon particles when the water migrates to the outer surfaces of the particles. The active components are uniformly distributed on the inner and outer surfaces of the active carbon particles, and the conditions that the active components are crystallized and run off and block the pore channels close to the outer surfaces of the active carbon particles in the drying and using processes are improved. Therefore, the catalyst has higher activity and longer service life. The life test also shows that the activity of the catalyst is low in reduction rate and slow in reduction.
3) Because the catalyst is dried in the rotary kiln, the catalyst material pile is turned over in the drying process and is heated uniformly, so that the reduction and even inactivation of the activity of the catalyst caused by overhigh local temperature in the drying process are avoided.
4) The drying and/or dipping processes are carried out in the rotary kiln, so that the long-time draining process required after dipping in a drying tower is avoided, the production capacity of equipment is improved, and the zinc acetate precipitation caused by temperature reduction during draining is avoided. Meanwhile, the phenomena of zinc acetate precipitation and inconsistent loading of active components at the upper part and the lower part of a bed layer caused by accumulated liquid at the lower part of a catalyst bed layer in a drying tower are avoided.
Through a plurality of improvements of the inventor of the application, the catalyst with high loading capacity can be applied to industrial production and industrial devices.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
A method for preparing a vinyl acetate catalyst by an acetylene method, wherein the catalyst takes active carbon as a carrier and zinc acetate as a main active component, and comprises the following steps:
step i) impregnation Process
The zinc salt and/or the cocatalyst component are prepared into a solution, and then the activated carbon support is impregnated with the solution, and the zinc salt and the cocatalyst component are impregnated on the activated carbon.
Step ii) drying process
And heating and drying the impregnated activated carbon to obtain the acetylene method vinyl acetate catalyst.
Wherein the impregnation step i) and the drying step ii) are performed in the same apparatus; this avoids crystallization and precipitation of the active ingredient due to a decrease in temperature of the activated carbon impregnated with the active ingredient during transfer from the impregnation tank to the drying rotary kiln. The working procedure of transferring the active carbon is also reduced.
The drying process of the step ii) is to feed current into the impregnated activated carbon, to make the activated carbon generate heat to complete the drying, and the activated carbon is stir-fried in the process.
The impregnation process of step i) above and the drying process of step ii) above can generally be accomplished in a rotary kiln.
The zinc salt is preferably zinc acetate, and can also be zinc nitrate, zinc chloride and/or organic acid zinc. In the process of preparing the aqueous solution, an organic solvent such as ethanol or acetic acid may be added.
In the step ii):
the method of feeding current into the impregnated activated carbon is to feed direct or alternating current into the activated carbon by directly connecting the electrodes of the power supply to the impregnated activated carbon, thereby heating the activated carbon. Alternatively, the current is fed to the impregnated activated carbon by means of alternating current induction.
And the activated carbon carrier is subjected to a plurality of impregnation processes and a plurality of drying processes. For example, because zinc nitrate has a particularly high solubility in water, the zinc nitrate and the promoter component can be impregnated first, and then the activated carbon is heated and dried at a relatively high temperature to decompose the zinc nitrate into zinc oxide. Then, acetic acid steam is used for reacting with the zinc oxide loaded on the active carbon to generate a zinc acetate active component; or the activated carbon loaded with zinc oxide is dipped again by a zinc acetate solution and then dried at a lower temperature, such as 100 ℃, to increase the loading of zinc on the activated carbon.
The acid groups of the zinc salt solution used in the above multiple impregnation processes are the same or different.
The highest temperature of the active carbon in the last drying process is 200 ℃ or below, and the highest temperature of the active carbon in the rest drying processes is higher than the decomposition temperature of the zinc salt in the previous impregnation process.
In the drying process, inert gas for reaction is introduced or vacuum suction is carried out to take the evaporated gas-phase material out of the device.
The technical scheme of the present invention can be further described by the following two preparation methods, but the technical scheme of the present invention is not limited to the two preparation methods.
The preparation method comprises the following steps: the preparation method comprises the steps of preparing an aqueous solution of active component zinc acetate and/or a cocatalyst component, immersing the active carbon into the aqueous solution, impregnating the active carbon with the zinc acetate and the cocatalyst component, placing the impregnated active carbon in a rotary kiln, electrically contacting the positive and negative electrodes of a heating power supply for drying with the impregnated active carbon, switching on the power supply to enable current to flow through the active carbon so as to enable the active carbon to generate heat, heating the active carbon to 50-250 ℃, and drying the water to about 10% to obtain a catalyst finished product. Due to the rotation of the rotary kiln in the drying process, the catalyst material pile is heated uniformly, the temperature is controlled more easily, and the catalyst deactivation caused by overheating is avoided.
The preparation method 2 comprises the following steps: the method comprises the steps of adding an activated carbon carrier into a rotary kiln, preparing an aqueous solution from the activated component zinc acetate and/or a cocatalyst component, pumping the aqueous solution into the rotary kiln filled with the activated carbon carrier, dipping the activated carbon with the zinc acetate and the cocatalyst component, placing the rotary kiln into an induction coil, passing an alternating current with a certain frequency through the induction coil, generating a corresponding induction current by the activated carbon in the rotary kiln, enabling the induction current to flow through the activated carbon to heat the activated carbon, heating the activated carbon to 50-250 ℃, and drying the moisture content to about 5% to obtain a catalyst finished product. The preferred material for the rotary kiln in this embodiment is a non-metallic material.
The following comparative examples 1, 1 and 2 are used to illustrate the technical solutions of the present invention:
comparative example 1
The activated carbon particles used as the carrier have a cylindrical shape, a diameter of about 2mm, a length of 2 to 5mm, and a bulk density of about 0.38 to 0.4g/ml (the same applies to the activated carbon in the following examples). Soaking 40ml of the activated carbon, 15.4g of dry weight and 100ml of 35 wt% zinc acetate solution at 95 ℃ for 60min, filtering, drying at 95 ℃ for 5h in an oven, and drying at 105 ℃ for 5 h. The zinc acetate crystals on the surfaces of the active carbon particles of the catalyst are found to be more. The catalyst prepared by the method has the reaction temperature of 175 ℃, the acetylene-acetic acid ratio of 6:1 and the space velocity of 300m3·h-1Vinyl acetate was synthesized under the conditions for activity examination. The average result of the 6h reaction was taken and the vinyl acetate space-time yield was 1.81g/ml cat/d (g per ml catalyst per day). Taking catalyst particles, separating the outer layer from the inner layer, crushing, and performing X-ray diffraction analysis respectively to find that the outer layer and the inner layer both have higher zinc acetate crystal diffraction peaks. In industrial production, the impregnated catalyst is dried by microwave, and the catalyst is sieved after drying to screen out zinc acetate crystals falling from the surfaces of active carbon particles. Loading 45m on an industrial installation3The space-time yield of the catalyst and the vinyl acetate can reach 2.3t/m3cat/d (ton per cubic meter of catalyst per day). However, the catalyst life on an industrial plant is only about 180 days.
Example 1
The diameter of the activated carbon particles is about 2mm, and the length of the activated carbon particles is 2-5 mm. Taking a volume of 2m3The activated carbon is loaded into a rotary kiln with a length of 2m3Soaking 35 wt% of zinc acetate and cocatalyst solution in the rotary kiln at 90 ℃ for 60min, draining for 20min, arranging a power supply anode at the rotary axis of the rotary kiln, taking a metal rotary pipe of the rotary kiln as a power supply cathode, connecting a 220V power supply live wire to the anode, connecting a zero line of a 220V power supply to the cathode, heating the soaked activated carbon to 95 ℃ within 40min, and preserving heat at 95-105 ℃ for 20min to finish the drying process. It was found that the surface of the catalyst activated carbon particles was almost free of vinegarThe zinc has a grain size and color, but a whiter surface than the non-impregnated activated carbon particles. The catalyst particles are taken and crushed for X-ray diffraction analysis, and no obvious zinc acetate crystal diffraction peak is found. Taking 40ml of the catalyst prepared by the method, observing the activity of the catalyst on an experimental device, wherein the reaction temperature is 175 ℃, the acetylene-acetic acid ratio is 6:1, and the space velocity is 300m3·h-1Vinyl acetate is synthesized under the condition, and the space-time yield of the vinyl acetate is 1.81 g/mlcat/d. Because the catalyst is turned over along with the rotation of the rotary kiln in the drying process, the appearance of the active carbon particles is uniform and consistent, and the dried catalyst can be easily discharged from the rotary kiln. And when the drying tower is used for dipping and drying, the draining time is generally controlled to be 3-9 h, more zinc acetate crystals are arranged on the surfaces of the catalyst activated carbon particles at the lower part of the drying tower, and the catalyst cannot stably run after being dried and discharged due to the fact that the zinc acetate crystals are adhered at the lower part of the drying tower.
Example 2
The activated carbon particles are cylindrical, the diameter is about 2mm, and the length is 2-5 mm. Taking a volume of 2m3The activated carbon is charged into a rotary kiln. The rotary pipe of the rotary kiln is made of epoxy resin, and a copper pipe coil is sleeved outside the rotary pipe. By 2m3Soaking activated carbon in 30 wt% zinc acetate solution at 90 deg.C for 60min, draining for 20min, rotating the rotary kiln, and introducing 1000Hz AC current into the copper tube coil to generate induced current in the activated carbon particle pile of the catalyst, which heats the soaked activated carbon to 130 deg.C and dries for 60 min; then 2m again3Soaking the activated carbon in 30 wt% zinc acetate solution at 90 deg.C for 60min, draining for 20min, rotating the rotary kiln again, introducing 1000Hz AC current into the copper tube coil to generate induced current in the activated carbon particle pile of the catalyst, and heating the secondarily soaked activated carbon to 105 deg.C for 60 min. The catalyst was discharged from the rotary kiln. The catalyst surface had no apparent zinc acetate white color. Taking 40ml of the catalyst prepared by the method, observing the activity of the catalyst on an experimental device, wherein the reaction temperature is 175 ℃, the acetylene-acetic acid ratio is 6:1, and the space velocity is 300m3·h-1Vinyl acetate is synthesized under the condition, and the space-time yield of the vinyl acetate is 1.94 g/mlcat/d. Because the catalyst is driedThe catalyst is turned over along with the rotation of the rotary kiln in the process, the appearance of the activated carbon particles is still uniform and consistent despite the secondary impregnation and drying, and the dried catalyst can be easily discharged from the rotary kiln.
In summary, the technical principle of the invention is that the drying and/or impregnation way in the catalyst preparation process is improved to inhibit the crystallization behavior of zinc acetate on the inner pores and the outer surface of the active carbon particles, thereby effectively improving the loading capacity of the active carbon on the active component zinc acetate, having high activity and long service life under the condition of maintaining high zinc acetate loading capacity, and remarkably improving the catalyst efficiency.
The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
Reference throughout this specification to "one embodiment," "another embodiment," "an embodiment," etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment described generally in this application. The appearances of the same phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is submitted that it is within the scope of the invention to effect such feature, structure, or characteristic in connection with other embodiments.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure and claims of this application. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.

Claims (8)

1. A method for preparing a vinyl acetate catalyst by an acetylene method comprises the following steps:
step i) impregnation Process
Preparing a zinc salt and/or a cocatalyst component into a solution, then impregnating an activated carbon carrier with the solution, and impregnating the zinc salt and the cocatalyst component on the activated carbon;
step ii) drying process
Heating and drying the impregnated activated carbon to obtain the acetylene method vinyl acetate catalyst;
wherein the impregnation step i) and the drying step ii) are performed in the same apparatus;
the drying process of the step ii) is to feed current into the impregnated activated carbon, to make the activated carbon generate heat to complete the drying, and the activated carbon is stir-fried in the process.
2. The method for preparing a vinyl acetate catalyst by an acetylene process according to claim 1, wherein the impregnation process of step i) and the drying process of step ii) are performed in a rotary kiln.
3. The method for preparing vinyl acetate catalyst by acetylene process according to any of claims 1-2, characterized in that in step ii):
the method of feeding current into the impregnated activated carbon is to feed direct or alternating current into the activated carbon by directly connecting the electrodes of the power supply to the impregnated activated carbon, thereby heating the activated carbon.
4. The method for preparing vinyl acetate catalyst by acetylene process according to any of claims 1-2, characterized in that in step ii):
the method of feeding current to the impregnated activated carbon is by means of alternating current induction.
5. The method for preparing the vinyl acetate catalyst by the acetylene method according to any one of claims 1 to 4, characterized in that the activated carbon carrier is subjected to a plurality of dipping processes and a plurality of drying processes.
6. The method for preparing a vinyl acetate catalyst by an acetylene method according to claim 5, characterized in that the acid groups of the zinc salt solution used for the multiple impregnation processes are the same or different.
7. The method for preparing a vinyl acetate catalyst by an acetylene process according to claim 5 or 6, wherein the maximum temperature to which the activated carbon is passed during the last drying process is 200 ℃ or less, and the maximum temperature to which the activated carbon is passed during the remaining drying process is higher than the decomposition temperature of the zinc salt during the previous impregnation process.
8. The method for preparing the vinyl acetate catalyst by the acetylene method according to any one of claims 1 to 7, characterized in that in the drying process, inert gas for reaction is introduced or vacuum suction is carried out to take the evaporated gas-phase material out of the device.
CN202110930543.3A 2021-08-13 2021-08-13 Method for preparing vinyl acetate catalyst by acetylene method Pending CN113649082A (en)

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CN103447084A (en) * 2012-05-31 2013-12-18 冯良荣 Catalyst for acetylene-method synthesis of vinyl acetate and preparation method thereof
CN108144648A (en) * 2018-01-29 2018-06-12 安徽皖维高新材料股份有限公司 A kind of preparation method of acetylene in gas phase method synthesizing vinyl acetate catalyst
CN109686982A (en) * 2019-01-29 2019-04-26 冯良荣 A method of preparing load type carbon nitride

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB808828A (en) * 1957-06-04 1959-02-11 Huels Chemische Werke Ag Improvements in the production of vinyl acetate
CN86107833A (en) * 1986-11-17 1988-07-20 吉林省化学纤维技术研究所 Zinc oxide catalytic agent for synthesizing of acetic acid ethylene
CN2855526Y (en) * 2005-12-20 2007-01-10 上海正海活性炭有限公司 Electric side heating rotary kiln (internal heating type) active carbon regeneration apparatus
CN102218340A (en) * 2010-04-16 2011-10-19 天华化工机械及自动化研究设计院 Preparation method for synthesizing vinyl acetate catalyst by using acetylene gas phase method
CN103111325A (en) * 2011-11-16 2013-05-22 上海浦景化工技术有限公司 Process for synthesizing vinyl acetate catalyst through acetylene method
CN103418411A (en) * 2012-05-25 2013-12-04 冯良荣 Preparation method of catalyst used for preparing vinyl chloride by acetylene hydrochlorination
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