CN111068777A - Regeneration method of waste catalyst for acetylene method vinyl acetate - Google Patents
Regeneration method of waste catalyst for acetylene method vinyl acetate Download PDFInfo
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- acetylene
- zinc
- acetate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 208
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 78
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 52
- 238000011069 regeneration method Methods 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 50
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004246 zinc acetate Substances 0.000 claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 177
- 239000012298 atmosphere Substances 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- HDJDFKVMYFWLIH-UHFFFAOYSA-N C#C.CC(=O)OC=C Chemical compound C#C.CC(=O)OC=C HDJDFKVMYFWLIH-UHFFFAOYSA-N 0.000 claims 2
- 230000008929 regeneration Effects 0.000 abstract description 31
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 74
- 239000011541 reaction mixture Substances 0.000 description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 25
- 229910052725 zinc Inorganic materials 0.000 description 25
- 239000011701 zinc Substances 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 238000005520 cutting process Methods 0.000 description 13
- 238000010926 purge Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 12
- 238000001994 activation Methods 0.000 description 11
- 230000004913 activation Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 but not limited to Chemical compound 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229940091251 zinc supplement Drugs 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a regeneration method of a waste catalyst of vinyl acetate by an acetylene method, which mainly solves the problems of regeneration and cyclic utilization of the waste catalyst. The invention adopts a regeneration method of a waste catalyst of vinyl acetate by an acetylene method, the waste catalyst comprises an active component and a carrier, the carrier is active carbon, the active component comprises zinc acetate, and the regeneration method comprises the following steps: (1) the technical proposal of the form of the regenerated catalyst zinc oxide is obtained by thermally treating the waste catalyst to convert the zinc acetate therein into the zinc oxide, which better solves the problem and can be used in the industrial production of acetylene-method vinyl acetate synthesis.
Description
Technical Field
The invention relates to a regeneration method of a waste catalyst of vinyl acetate by an acetylene method.
Background
Vinyl acetate, abbreviated as Vinyl Acetate (VAM), is an important organic chemical raw material, is mainly used for producing derivatives such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), vinyl acetate-ethylene copolymer emulsion (VAE) or copolymer resin (EVA), vinyl acetate-vinyl chloride copolymer (EVC), polyacrylonitrile comonomer, acetal resin and the like, and has wide development and utilization values in the aspects of coating, slurry, adhesive, vinylon, film, leather processing, synthetic fiber, soil improvement and the like.
At present, the main production process routes of vinyl acetate are an ethylene method and an acetylene method. The European and American countries mainly adopt an ethylene process route, and the national coal resources are rich and the petroleum resources are deficient, so that the acetylene process route is mainly adopted at present. The process route of the acetylene method adopts zinc acetate loaded active carbon as a catalyst, the catalyst is simple to prepare and low in cost, but the catalyst also has the defects of low activity, short service life and the like, and the service life is usually 250-300 days. The waste vinyl acetate catalyst is mainly treated in a physical landfill mode, so that not only is the resource waste greatly caused, but also the heavy metal pollution is caused. Under the increasingly strict environmental protection policy in China, the recycling of the waste catalyst of the acetylene method vinyl acetate has important significance.
At present, researches on recycling of zinc acetate/activated carbon waste catalysts are still active at home and abroad. Representative foreign research works include: respectively adopting organic solvent extraction and supercritical CO extraction for Dabek2The extraction method and the microwave-assisted leaching method separate and recycle the waste catalyst, and the leaching rates of zinc reach 72.3%, 92.7% and more than 94% respectively. But also has the problems of difficult recycling of the organic solvent, strict equipment requirement of the acid leaching solution, higher process cost, small sample treatment capacity of microwave equipment, high cost, strict equipment requirement and the like. The typical works in the country are: the project group of professor Pengjinhui of Kunming theory of engineering university adopts microwave radiation to pretreat the waste catalyst, then selects ammonium salt as leaching agent to leach zinc from the pretreated waste catalyst, and then obtains zinc oxide and active carbon through the procedures of distillation crystallization, zinc oxide preparation, active carbon regeneration and the like. The method has high zinc leaching rate (95.79%), and large specific surface area of regenerated activated carbon (1560 m)2Per gram) to reach the commercial grade standard. However, the method also has the problems that the flow is long, the microwave equipment is difficult to enlarge, and the like, and has not been reported industrially so far.
The research aims to adopt the acetylene method vinyl acetate waste catalyst, obtain a regenerated catalyst zinc oxide form through heat treatment, contact the zinc oxide with a material containing acetic acid to convert at least part of the zinc oxide into zinc acetate, and supplement the zinc acetate according to the actual condition to obtain a catalyst zinc acetate form and use the catalyst in the acetylene method to synthesize vinyl acetate. The method for regenerating and utilizing the acetylene method vinyl acetate catalyst is not reported so far.
Disclosure of Invention
The invention aims to solve the technical problem that the waste catalyst in the prior art cannot be recycled, and provides a regeneration method of an acetylene-method vinyl acetate catalyst.
The second technical problem to be solved by the present invention is to provide a regenerated catalyst.
The invention also provides a method for synthesizing vinyl acetate by adopting the regenerated catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the regeneration method of the acetylene method vinyl acetate waste catalyst comprises an active component and a carrier, wherein the carrier is active carbon, the active component comprises zinc acetate, and the regeneration method comprises the following steps:
(1) and (4) thermally treating the waste catalyst to convert zinc acetate in the waste catalyst into zinc oxide, thereby obtaining the regenerated catalyst zinc oxide form.
In the above technical solution, the atmosphere for the heat treatment preferably comprises CO and H2、He、Ne、Ar、N2、CO2、H2O and NH3At least one substance of the group of substances.
In the above embodiment, the atmosphere for the heat treatment more preferably comprises N2、CO2And H2At least two substances of the group consisting of O, e.g. the atmosphere under which the heat treatment is carried out comprises N2And CO2Two substances; further, for example, the atmosphere for the heat treatment includes N2And H2O two substances; further, for example, the atmosphere for heat treatment includes CO2And H2And O, the two substances have a synergistic effect on the improvement of the space-time yield of the regenerated catalyst. The ratio between the two substances at this time is not particularly limited as long as the atmosphere including both of the above substances can achieve a comparable synergistic effect. As non-limiting examples, the molar ratio between the two substances is 0.1 to 10, and within this range, non-limiting examples of more specific values of the molar ratio may be 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, etc.
In the above technical solution, the temperature of the heat treatment is preferably 400-. For example, but not limited to, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, etc. More preferably 450 ℃ and 950 ℃.
In the technical scheme, the time of the heat treatment is preferably 0.5-10 h. Such as but not limited to 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5 h.
In the above technical solution, the heat treatment method specifically adopted for the heat treatment is not particularly limited, and those commonly used in the art can be selected to achieve comparable technical effects without creative efforts, for example, the treatment method adopts a conventional heat transfer method (heat convection, heat radiation, heat conduction, etc.), and the commonly used equipment can be a roasting furnace, etc.
The regenerated catalyst zinc oxide obtained by the step (1) can be directly supplied to the market. However, when the zinc oxide catalyst is directly used in an acetylene-process vinyl acetate device, an induction period is required, acetic acid in a reaction material contacted with zinc oxide is gradually converted into zinc acetate in the induction period, and then normal catalytic activity can be exerted. Or, therefore, the activated carbon loaded zinc oxide is not convenient for the application customers of the regenerated catalyst.
In order to facilitate the use of the regenerated catalyst, the present invention preferably further comprises the steps of:
(2) contacting said zinc oxide with a material containing acetic acid to convert at least a portion of said zinc oxide to zinc acetate, and preferably to convert all of said zinc oxide to zinc acetate.
In the using process of the fresh catalyst, the zinc acetate is often lost due to the conditions of material scouring, entrainment and the like, and the invention also comprises the following steps in order to increase the content of active components of the catalyst:
(3) and supplementing zinc acetate.
When the present invention includes step (3), step (3) is performed after step (1);
when the method comprises the step (2) and the step (3), the step (3) can be carried out before the step (2), or the step (3) is carried out after the step (2), or the step (2) and the step (3) can be carried out simultaneously, and both the steps can achieve comparable technical effects. In the case of simultaneously performing the step (2) and the step (3), for example, a material containing acetic acid and zinc acetate (such as, but not limited to, a mixed aqueous solution of acetic acid and zinc acetate) is simultaneously mixed with the product in the form of the activated carbon loaded with zinc oxide obtained in the step (1).
In the technical scheme, the essence of the inactivation of the waste catalyst is that the catalyst is in contact with an acetylene method vinyl acetate reaction system for a long time, so that the regeneration method is irrelevant to whether the acetylene method vinyl acetate reaction system adopts a fixed bed acetylene method vinyl acetate process or a fluidized bed acetylene method vinyl acetate process, in other words, the waste catalyst provided by the invention can be derived from the fixed bed acetylene method vinyl acetate process or the fluidized bed acetylene method vinyl acetate process.
In the long-term use of fresh catalyst, the activity of catalyst will gradually decrease, and different manufacturers generally consider the degree of decrease of catalyst activity, the loss of production efficiency caused during the catalyst replacement, and the increase of production efficiency caused by the replacement of new catalyst, and consider the timing at which the used catalyst is treated as the waste catalyst. The method of the invention is feasible for regenerating the waste catalyst at any time understood by the technical field, and can achieve comparable technical effects. As a practical opportunity for some manufacturers to find out, and as a non-limiting example of the present invention, a catalyst which, when used in an acetylene-process vinyl acetate process, has a reaction temperature of 196 ℃ as compared with a fresh catalyst, has a catalyst space-time yield which is reduced by more than 30% is used as a spent catalyst. In order to facilitate the comparison, the waste catalysts in the embodiment of the invention are all the catalysts which adopt the fixed bed process and reduce the space-time yield of the catalyst by 48 percent when the reaction temperature of the waste catalyst of the acetylene method vinyl acetate reaches 196 ℃.
To solve the second technical problem, the technical solution of the present invention is as follows:
a regenerated catalyst obtained by the regeneration method according to any one of the above-mentioned aspects.
To solve the third technical problem, the technical scheme of the invention is as follows: the vinyl acetate synthesis method takes acetic acid and acetylene as raw materials, and the vinyl acetate is generated by reaction in the presence of the regenerated catalyst in the second technical scheme of the technical problems.
The reaction temperature in the technical scheme is preferably 160-200 ℃.
The pressure of the reaction in the technical scheme is preferably 0.1-0.5 atm.
Unless otherwise specified, all pressures recited herein are in terms of gauge pressure.
In the technical scheme, the raw material composition is preferably acetylene, acetic acid (5-12): 1 in terms of molar ratio.
In the technical scheme, the preferred volume space velocity of the raw material is 250-350 h-1。
The contents of all components in the reaction product are analyzed by a gas chromatography-mass spectrometer (GC-MS), and the space-time yield of the vinyl acetate of the catalyst is calculated.
Compared with the prior art, the key point of the invention is that the regeneration of the acetylene method vinyl acetate waste catalyst is simply and rapidly realized through the steps of simple thermal activation and the like, the vinyl acetate catalyst is prepared again, and no new three wastes are discharged. Is favorable for reducing the pollution of the waste catalyst to the environment, and provides a green and circular catalyst regeneration method.
The experimental result shows that the regenerated catalyst has the vinyl acetate space-time yield of 110.2 g/(L.h), obtains better technical effect, and particularly selects CO in the regeneration thermal activation process of the waste catalyst2，H2O，N2When the mixed atmosphere of two or more than two kinds is used for heat treatment, more outstanding technical effects are obtained, and the method can be used in the industrial production of vinyl acetate. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in CO2In the atmosphere (pressure: 30kPa, volume space velocity: 21.6h-1) And (3) carrying out heat treatment at 400 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
Mixing 200ml of regenerated catalyst zinc oxide form with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 50g/L, and the concentration of the acetic acid is 10g/L) in a 500ml conical flask, placing the conical flask in a water bath oscillator, oscillating for 3h at 80 ℃, and placing the conical flask in a blast drying oven to dry for 3h at 120 ℃ to obtain the regenerated catalyst zinc acetate form. The zinc content of the catalyst was determined by ICP to be 58.6 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 60.1 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 2 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in CO2In the atmosphere (pressure: 30kPa, volume space velocity: 21.6h-1) And (3) carrying out heat treatment at 1000 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 250g/L, and the concentration of the acetic acid is 100g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 94.4 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 70.3 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 3 ]
1. Regeneration of waste catalyst
500ml of acetylene method ethyl acetate dried at 120 ℃ for 3 hoursThe alkene waste catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) is placed in a tubular atmosphere activation furnace and is subjected to CO reaction2In the atmosphere (pressure: 30kPa, volume space velocity: 21.6h-1) And (3) carrying out heat treatment at 800 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 80.5 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 4 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in H2In an O atmosphere (pressure: 30kPa, volume space velocity: 21.6 h)-1) And (3) carrying out heat treatment at 800 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 85.4 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 5 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in N2In the atmosphere (pressure: 30kPa, volume space velocity: 21.6h-1) And (3) carrying out heat treatment at 800 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 75.6 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 6 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in NH3In the atmosphere (pressure: 30kPa, volume space velocity: 21.6h-1) And (3) carrying out heat treatment at 800 ℃ for 3h, cooling and taking out to obtain the regenerated catalyst zinc oxide form.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid is 5:1, after the reaction is continued for 48 hours,the reaction was stopped.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 70.9 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 7 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in CO2And N2In a mixed atmosphere (pressure: 30kPa, volume space velocity: 21.6 h)-1，CO2/N2The molar ratio is as follows: 1/1) and heat treatment is carried out for 3h at 800 ℃, and the regenerated catalyst zinc oxide form is obtained after cooling and taking out.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 95.8 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 8 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in CO2And H2In a mixed atmosphere of O (pressure: 30kPa, volume space velocity: 21.6 h)-1，CO2/H2Molar ratio of O: 10/1) and heat treatment is carried out for 3h at 800 ℃, and the regenerated catalyst zinc oxide form is obtained after cooling and taking out.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 99.8 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 9 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (analyzed by ICP-AES) dried at 120 ℃ for 3 hoursZinc content 43.2g/L), placing in a tubular atmosphere activation furnace, and reacting in CO2And H2In a mixed atmosphere of O (pressure: 30kPa, volume space velocity: 21.6 h)-1，CO2/H2Molar ratio of O: 1/1) and heat treatment is carried out for 3h at 800 ℃, and the regenerated catalyst zinc oxide form is obtained after cooling and taking out.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 110.2 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 10 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in CO2And H2In a mixed atmosphere of O (pressure: 30kPa, volume space velocity: 21.6 h)-1，CO2/H2Molar ratio of O: 1/10) and heat treatment is carried out for 3h at 800 ℃, and the regenerated catalyst zinc oxide form is obtained after cooling and taking out.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 97.4 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ example 11 ]
1. Regeneration of waste catalyst
500ml of acetylene-method vinyl acetate spent catalyst (the zinc content of which is 43.2g/L by ICP-AES analysis) dried at 120 ℃ for 3 hours is taken and placed in a tubular atmosphere activation furnace in H2O and N2In a mixed atmosphere (pressure: 30kPa, volume space velocity: 21.6 h)-1，H2O/N2The molar ratio is as follows: 1/1) and heat treatment is carried out for 3h at 800 ℃, and the regenerated catalyst zinc oxide form is obtained after cooling and taking out.
200ml of regenerated catalyst zinc oxide form is taken and mixed with 250ml of acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a blast drying oven to be dried for 3h at the temperature of 120 ℃, so that the regenerated catalyst zinc acetate form is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 90.2 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
2. Synthesis of vinyl acetate
40ml of spent catalyst was charged in a 100ml fixed bed reactor with N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 20.9 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
1. Regeneration of waste catalyst
200ml of the waste catalyst is mixed with 250ml of an acetic acid solution of zinc acetate (the concentration of the zinc acetate is 150g/L, and the concentration of the acetic acid is 56g/L) in a 500ml conical flask, the conical flask is placed in a water bath oscillator, the conical flask is oscillated for 3h at the temperature of 80 ℃, and the conical flask is placed in a forced air drying oven to be dried for 3h at the temperature of 120 ℃, so that the form of the regenerated catalyst zinc acetate is obtained. The zinc content of the catalyst was determined by ICP to be 83.1 g/L.
2. Synthesis of vinyl acetate
40ml of catalyst are charged in a 100ml fixed bed reactor, using N2After leakage testing, use N2Fully purging the system, and after the system is heated up, closing N2Sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 180 ℃ and the reaction pressure (gauge pressure) to be 0.3 atm; volume space velocity of raw materials: 300h-1(ii) a The raw materials comprise: the molar ratio of acetylene to acetic acid was 5:1, and the reaction was stopped after a further 48h of reaction.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst vinyl acetate space time yield was 25.5 g/(L.h), and for convenience of illustration and comparison, the catalyst regeneration process conditions and the catalyst vinyl acetate space time yield are shown in Table 1.
As can be seen from the comparison between the comparative example 1 and the examples 1 to 11, the catalytic performance of the waste catalyst is remarkably improved compared with that of the waste catalyst after the regeneration treatment.
From comparative example 2 and examples 1 to 11, comparative example 1 shows that the catalyst performance of the catalyst sample obtained by directly impregnating the spent catalyst with the active component without heat treatment is only slightly higher than that of the spent catalyst and is much lower than that of the catalyst sample subjected to the whole catalyst regeneration step.
The catalyst obtained by heat-treating the spent catalyst in 2 or more atmospheres has better catalytic performance because different atmospheres produce synergistic effects during the heat-treatment of the spent catalyst, as shown in the same ratios of examples 7, 9 and 11 to examples 3, 4 and 5. Further, CO is used2And H2And carrying out heat treatment on the waste catalyst in the O mixed atmosphere to further prepare the catalyst with the best catalytic performance.
TABLE 1
Claims (10)
1. The regeneration method of the acetylene method vinyl acetate waste catalyst comprises an active component and a carrier, wherein the carrier is active carbon, the active component comprises zinc acetate, and the regeneration method comprises the following steps:
(1) and (4) thermally treating the waste catalyst to convert zinc acetate in the waste catalyst into zinc oxide, thereby obtaining the regenerated catalyst zinc oxide form.
2. The regeneration method as set forth in claim 1, wherein the atmosphere for the heat treatment includes an atmosphere selected from the group consisting of CO and H2、He、Ne、Ar、N2、CO2、H2O and NH3At least one substance of the group of substances.
3. The regeneration method as claimed in claim 1, wherein the temperature of the heat treatment is 400-1000 ℃.
4. The regeneration method as claimed in claim 3, wherein the temperature of the heat treatment is 450-950 ℃.
5. The recycling method according to claim 1, wherein the heat treatment time is 0.5 to 10 hours.
6. The regeneration method according to claim 1, further comprising the steps of:
(2) contacting the zinc oxide with a material comprising acetic acid to at least partially convert the zinc oxide to zinc acetate.
7. The regeneration method according to any one of claims 1 to 6, further comprising the steps of:
(3) and supplementing zinc acetate.
8. The regeneration method as claimed in claim 1, wherein the spent catalyst is derived from a fixed bed acetylene vinyl acetate process or a fluidized bed acetylene vinyl acetate process.
9. A regenerated catalyst obtained by the regeneration method according to any one of claims 1 to 8.
10. A method for synthesizing vinyl acetate, which comprises reacting acetic acid and acetylene as raw materials in the presence of the regenerated catalyst of claim 9 to obtain vinyl acetate.
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