CN107774305B - Catalyst for vinyl acetate production - Google Patents

Catalyst for vinyl acetate production Download PDF

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CN107774305B
CN107774305B CN201610750116.6A CN201610750116A CN107774305B CN 107774305 B CN107774305 B CN 107774305B CN 201610750116 A CN201610750116 A CN 201610750116A CN 107774305 B CN107774305 B CN 107774305B
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catalyst
vinyl acetate
content
reaction mixture
activated carbon
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CN107774305A (en
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邱鹏远
杨运信
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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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
    • B01J31/02—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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a catalyst for vinyl acetate production and a preparation method thereof, and mainly solves the problem of high content of byproduct benzene in the prior art. The invention adopts the catalyst for vinyl acetate production, the catalyst adopts the active carbon as the carrier, the active component comprises zinc acetate and a cocatalyst, and the cocatalyst comprises at least one element selected from iron series metal elements.

Description

Catalyst for vinyl acetate production
Technical Field
The invention relates to an acetylene gas phase method vinyl acetate catalyst, a preparation method of the catalyst and a synthetic method of vinyl acetate.
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. With the continuous progress of production technology, the application field is still expanding.
The worldwide vinyl acetate production in 2011 reaches 743.4 million tons/year, and is mainly concentrated in Asia, North America and Western Europe. According to regional capacity statistics, Asia Tai is 398.8 ten thousand tons/year, accounting for 53.6%; north america at 206.3 ten thousand tons/year, accounting for 27.8%; western Europe is 117.1 ten thousand tons/year, accounting for 15.8%; the other areas account for 2.9%. Wherein the yield of the Chinese vinyl acetate is 216.5 ten thousand tons/year.
At present, the main production process routes of vinyl acetate are an ethylene method and an acetylene method. The acetylene method comprises a natural gas acetylene method and a calcium carbide acetylene method. The natural gas acetylene method adopts a fixed bed process, and selects granular zinc acetate/active carbon catalyst; the calcium carbide acetylene method adopts a fluidized bed process and selects powdery zinc acetate/active carbon catalyst. Because of different resource structures, countries and regions such as North America, Western Europe, Nippon singapore and the like basically adopt an ethylene process, while countries and regions such as Korea and India all adopt an acetylene process, and countries and regions such as China, Russia, eastern Europe and the like coexist. With the discovery of new natural gas and shale gas resources in China and the maturity and perfection of the exploitation technology thereof, the natural gas acetylene method vinyl acetate production process has very good prospects in China.
In 1922, Wacker Germany firstly used a method for synthesizing VAM from acetylene in a gas phase, and then the VAM 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. The catalyst has the disadvantages of rapid activity reduction, low production capacity, increased by-products along with the increase of reaction temperature and short service life of the catalyst. Meanwhile, the acetylene method has the advantages of simple technology, cheap and easily obtained catalyst, good activity, high selectivity, low construction cost and the like. Therefore, how to effectively improve the activity and service life of the catalyst becomes an important scientific problem in the field of catalysis, researchers in various countries start to systematically research the problem from aspects of selection and modification of active components, promoters, carriers, catalyst preparation processes and the like, and certain stage results are obtained.
For example, Japanese scholars propose two-component oxides (V 2 O 5 -ZnO, Fe 2 O 3 -ZnO) or three-component oxides (16ZnO 32Fe 2 O 3. V 2 O 5 and 24ZnO 8Cr 2 O 3. V 2 O 5) as active components of catalysts, although the catalysts have higher activity than Zn (OAc) 2/C catalysts under 250 catalysis, industrialization cannot be realized due to the disadvantages of high reaction temperature, high cost, rapid activity reduction and the like.
For example, Chinese patent (CN 1903435A, a catalyst for vinyl acetate synthesis and a preparation method thereof) selects bismuth subcarbonate as the cocatalyst, so that the space-time yield of vinyl acetate of the catalyst is increased from 2.02t/m 3 d to 2.67t/m 3 d, and the catalyst activity is increased by 32.2%.
For a long time, many scholars at home and abroad have not succeeded in experiments of replacing the activated carbon carrier with silica gel, alumina, aluminum silicate, molecular sieve and the like. The studies in the literature (chemical engineering, 1962,85(16): 1; petrochemical, 1979, (8)7:49) have found that the catalyst activity is much lower than that of the activated carbon supported catalyst when silica gel, alumina, aluminum silicate and molecular sieves are used as the carriers. Practice proves that the activated carbon is not replaceable as a carrier of the acetylene method vinyl acetate catalyst. Meanwhile, researchers consider modifying the activated carbon carrier, so that the purpose of improving the performance of the carrier is achieved. For example, the activity of the catalyst prepared by using activated carbon with 15 percent of nitric acid by mass as a carrier is improved by 5.36 percent compared with the catalyst prepared by using untreated activated carbon as a carrier by the research of documents (petrochemical industry, 2004,33(11): 1024). Chinese patent CN 102029193A, an active carbon used as a catalyst carrier and a treatment method and application thereof, selects hydrogen peroxide to carry out pretreatment on the active carbon carrier, and the result shows that the catalytic activity of the catalyst prepared by the active carbon treated by the method is improved by 2-15%. Chinese patent (CN 102284304a, a preparation method of a high-efficiency catalyst for synthesizing vinyl acetate by an acetylene method) selects a series of oxidants such as sulfuric acid, potassium permanganate, and ammonium persulfate in addition to hydrogen peroxide to pretreat activated carbon for preparation of a catalyst for synthesizing vinyl acetate. Although the activity of the catalyst can be improved to a certain extent by selecting the oxidant to carry out pretreatment on the activated carbon carrier, most of the activated carbon treated by the acid or other oxidants needs to be washed and extracted for a long time to make the activated carbon neutral, the drying time is long, and the production time and the cost of the catalyst are increased.
With the recent continuous operation of new and expanded vinyl acetate plants in China, the market of vinyl acetate in China has become saturated and even has been in excess. Therefore, how to develop the downstream market of vinyl acetate is urgent to develop a downstream product of vinyl acetate with high added value. And improving the quality of the vinyl acetate product is one of the important precondition factors for developing downstream products with high added value.
Vinyl acetate is used for synthesizing vinyl acetate-ethylene copolymer (VAE) emulsion which is used for cigarette glue in the cigarette production process, but at present, only the ethylene vinyl acetate product index in China reaches the quality requirement of the cigarette glue used in the cigarette industry. The vinyl acetate product produced by the acetylene method contains a small amount of byproduct benzene (<5ppmw), so that the application of the vinyl acetate product to the production of the cigarette adhesive raw material VAE emulsion is restricted, and the problem of how to reduce the byproduct benzene in the vinyl acetate product produced by the acetylene method becomes a core problem restricting the application of the vinyl acetate product to the cigarette adhesive raw material. The research work of academia and industry on the acetylene method vinyl acetate catalyst mainly focuses on improving the catalyst activity, the catalyst service life and the like, and the problem of improving the selectivity of the catalyst, particularly reducing the content of the byproduct benzene, is not reported.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of high content of byproduct benzene in the prior art, and provides a novel vinyl acetate catalyst which has the characteristic of low content of generated byproduct benzene.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The third technical problem to be solved by the present invention is to provide a method for synthesizing vinyl acetate by using the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for vinyl acetate production adopts active carbon as a carrier, the active component comprises zinc acetate and a cocatalyst, and the cocatalyst comprises at least one element selected from iron series metal elements.
The addition of the iron-series metal element reduces the content of benzene impurity in the product.
In the technical scheme, the catalyst composition can contain no alkali metal acetate, for example, potassium acetate, and the alkali metal acetate causes the content of harmful impurity benzene in the product to be increased.
In the above technical scheme, the activated carbon is preferably at least one of coal activated carbon, coconut shell activated carbon, apricot shell activated carbon and bamboo activated carbon.
In the technical scheme, the specific surface area of the activated carbon is preferably 1000-1500 m 2/g, and the adsorption pore volume is preferably 0.50-1.00 cm 3/g.
In the above technical solution, the iron-based metal element is selected from at least one of iron, cobalt and nickel, and more preferably includes both cobalt and nickel.
In the above technical solution, the cocatalyst further includes at least one metal element selected from IVB elements in addition to the iron-based element.
In the above embodiment, the group IVB element is preferably at least one selected from titanium, zirconium and hafnium, and more preferably includes both zirconium and hafnium.
In the above technical solution, when the iron-based metal element at least includes Co or Ni, and the group IVB element at least includes Ha, the two group elements have synergistic effect in reducing the content of impurity benzene in the product. It is noted that no such synergy is found between Co and Zr, Ni and Zr.
In the technical scheme, when the iron-based metal elements at least comprise Co and Ni and the IVB group elements at least comprise Ha or Zr, the Co and the Ni have synergistic effect on reducing the content of impurity benzene in the product.
In the technical scheme, when the iron-based metal elements at least comprise Co and Ni, and the IVB group elements at least comprise Ha and Zr, the Ha and the Zr have synergistic effect on the aspect of reducing the content of impurity benzene in the product.
In the technical scheme, the content of the zinc acetate in the catalyst is preferably 50-300 g/L, and more preferably 80-200 g/L.
In the technical scheme, the content of the cocatalyst in the catalyst is preferably 0.45-7.50 g/L, and more preferably 1.00-5.00 g/L.
To solve the second technical problem, the technical solution of the present invention is as follows: the method for producing the catalyst in the technical scheme of one of the technical problems comprises the following steps:
Mixing zinc acetate and cocatalyst solution with carrier according to the composition of catalyst.
Drying.
In the above technical scheme, as non-limiting examples, the corresponding compound form of the cocatalyst can be:
The compound of the iron-based metal element is preferably at least one selected from the group consisting of ferrous acetate, ferrocene, ferric chloride, ferric sulfate, cobalt carbonyl, cobalt acetate, cobalt chloride, cobalt nitrate, nickel carbonyl, nickel acetate, nickel nitrate, nickel sulfate and nickel chloride, and more preferably at least one selected from the group consisting of cobalt acetate and nickel acetate; the compound of the group IVB element is preferably at least one selected from ammonium fluorotitanate, hexafluorotitanic acid, ammonium zirconium carbonate, ammonium fluorozirconate, ammonium fluorohafnate, and hafnium oxychloride, and more preferably at least one selected from ammonium fluorozirconate and ammonium fluorohafnate.
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 catalyst in any one of the technical schemes of the technical problems.
-1The key point of the invention is the selection of a catalyst, and a person skilled in the art knows how to determine a proper reaction temperature, reaction time, reaction pressure and material ratio according to actual needs.
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 active component of the catalyst comprises zinc acetate and a compound of at least one metal element selected from iron series metal elements and IVB group elements, which is beneficial to improving the selectivity of the catalyst and reducing the content of byproduct benzene in the product.
The experimental result shows that when the catalyst is adopted, the space-time yield of the vinyl acetate of the catalyst reaches 77.2 g/(L.h), the benzene content in the reaction mixture is reduced to 1620ppbw, and a better technical effect is obtained, particularly when the active component in the catalyst simultaneously comprises zinc acetate, at least one metal element compound selected from iron series metal elements and at least one metal element compound selected from IVB group elements, a more outstanding technical effect is obtained, and the catalyst can be used in the industrial production of the vinyl acetate. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and 2.70g of Ha-containing ammonium fluorohafnate ((NH 4) 2 HaF 6) in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH value of 4.8, soaking 1L of cylindrical coal activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the ICP content of the catalyst is measured to be 101g/L, and the Ha content is 2.70 g/L.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 77.2 g/(L.h), the benzene content in the reaction mixture was 1620 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 2 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and ferrous acetate (C 4 H 6 FeO 4) containing 2.70g of Fe in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH value of 4.8, immersing 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the Zn content of the catalyst is 101g/L and the Fe content is 2.70g/L through ICP measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by using a gas chromatography-mass spectrometer (GC-MS).
The calculated catalyst space time yield of vinyl acetate was 76.3 g/(L.h), and the benzene content in the reaction mixture was 3450 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
The preparation of the catalyst comprises the steps of dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) in an acetic acid water solution to obtain an impregnation liquid with the pH value of 4.8, impregnating 1L of cylindrical active carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H and drying at 110 ℃ to obtain the catalyst, and measuring the content of the zinc acetate in the catalyst to be 101g/L by ICP (inductively coupled plasma) measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to 178 ℃, the reaction pressure to be 0.25atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 63.2 g/(L.h), the benzene content in the reaction mixture was 5520 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 6.80g of potassium acetate (C 2 H 3 KO 2) and 2.70g of Fe-containing ferrous acetate (C 4 H 6 FeO 4) in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH value of 4.8, immersing 1L of cylindrical coal activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H and drying at 110 ℃ to obtain the catalyst, and measuring the zinc acetate content of 101g/L, the potassium acetate content of 6.80g/L and the Fe content of 2.70g/L by ICP.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 84.8 g/(L.h) and the benzene content in the reaction mixture was 5420 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 3 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and 2.70g of Co-containing cobalt acetate (C 4 H 6 CoO 4) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH value of 4.8, impregnating 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L and the Co content of the catalyst is 2.70g/L through ICP measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 78.9 g/(L.h), and the benzene content in the reaction mixture was 3050 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 4 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and nickel acetate containing 2.70g of Ni (C 4 H 6 NiO 4) in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH value of 4.8, impregnating 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L and the Ni content is 2.70g/L through ICP measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 76.9 g/(L.h), and the benzene content in the reaction mixture was 3280 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 5 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and 2.70g of ammonium fluotitanate containing Ti ((NH 4) 2 TiF 6) in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH value of 4.8, immersing 1L of cylindrical coal activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L and the Ti content is 2.70g/L through ICP measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The space time yield of vinyl acetate of the catalyst was calculated to be 72.5 g/(L.h) and the benzene content in the reaction mixture was 2550 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 6.80g of potassium acetate (C 2 H 3 KO 2) and 2.70g of Ti-containing ammonium fluotitanate ((NH 4) 2 TiF 6) in an acetic acid water solution to obtain 350ml of impregnation liquid with the pH of 4.8, immersing 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H and drying at 110 ℃ to obtain the catalyst, and measuring the zinc acetate content of 101g/L, the potassium acetate content of 6.80g/L and the Ti content of 2.70g/L by ICP.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 84.5 g/(L.h) and the benzene content in the reaction mixture was 7900 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 6 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn) and 2.70g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH of 4.8, soaking 1L of cylindrical coal activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L and the Zr content is 2.70g/L through ICP measurement.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The catalyst has a calculated vinyl acetate space-time yield of 73.4 g/(L.h) and a benzene content in the reaction mixture of 1980 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
The catalyst is prepared by mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 6.80g of potassium acetate (C 2 H 3 KO 2) and 2.70g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6) in an acetic acid aqueous solution sufficiently to obtain 350ml of an impregnation solution with the pH of 4.8, immersing 1L of a cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation solution, standing for 3H and drying at 110 ℃ to obtain the catalyst, and measuring the zinc acetate content of 101g/L, the potassium acetate content of 6.80g/L and the Zr content of 2.70g/L by ICP.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 84.6 g/(L.h), the benzene content in the reaction mixture was 7210 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 7 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Ha-containing ammonium fluorohafnate ((NH 4) 2 HaF 6) and 0.90g of Co-containing cobalt acetate (C 4 H 6 NiO 4) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH value of 4.8, soaking 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L, the Ha content of 1.80g/L and the Co content of 0.90g/L are measured by ICP.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The catalyst had a calculated vinyl acetate space-time yield of 78.1 g/(L.h) and a benzene content in the reaction mixture of 1320 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 8 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Ha-containing ammonium fluorohafnate ((NH 4) 2 HaF 6) and 0.90g of Ni-containing nickel acetate (C 4 H 6 NiO 4) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH value of 4.8, soaking 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L, the Ha content of 1.80g/L and the Ni content of 0.90g/L are measured by ICP.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 77.0 g/(L.h), the benzene content in the reaction mixture was 1230 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 5 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6) and 0.90g of Co-containing cobalt acetate (C 4 H 6 CoO 4) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH value of 4.8, immersing 1L of cylindrical coal-based activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H and drying at 110 ℃ to obtain the catalyst, wherein the ICP content of the catalyst is 101g/L, the Zr content is 1.80g/L and the Co content is 0.90 g/L.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
Analysis of the reaction mixture: the reaction mixture obtained by the above reaction was analyzed by gas chromatography-mass spectrometer (GC-MS).
The space time yield of vinyl acetate of the catalyst was calculated to be 75.1 g/(L.h) and the benzene content of the reaction mixture was 2550 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ COMPARATIVE EXAMPLE 6 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6) and 0.90g of Ni-containing nickel acetate (C 4 H 6 NiO 4) in an acetic acid aqueous solution to obtain 350ml of impregnation liquid with the pH value of 4.8, immersing 1L of cylindrical coal briquette carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation liquid, standing for 3H, and drying at 110 ℃ to obtain the catalyst.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 74.3 g/(L.h), and the benzene content in the reaction mixture was 2780 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 9 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Ha-containing ammonium fluorohafnate ((NH 4) 2 HaF 6), 0.60g of Co-containing cobalt acetate (C 4 H 6 CoO 4) and 0.30g of Ni-containing nickel acetate (C 4 H 6 NiO 4) in an acetic acid aqueous solution to obtain 350ml of an impregnation solution with the pH of 4.8, and immersing 1L of a cylindrical coal activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g in the impregnation solution, standing for 3H and drying at 110 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 101g/L, the Ha content is 1.80g/L, the Co content is 0.60g/L, and the Ni content is 0.30g/L through ICP determination.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 77.5 g/(L.h) and the benzene content in the reaction mixture was 940 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 10 ]
101g of zinc acetate (C 4 H 6 O 4 Zn), 1.80g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6), 0.60g of Co-containing cobalt acetate (C 4 H 6 CoO 4) and 0.30g of Ni-containing nickel acetate (C 4 H 6 NiO 4) are fully mixed and dissolved in an acetic acid aqueous solution to obtain 350ml of an impregnation solution with the pH of 4.8, and 1L of a cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200m 2/g is impregnated in the impregnation solution and is dried at the temperature of 110 ℃ after standing for 3H to obtain the catalyst.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 75.1 g/(L.h) and the benzene content in the reaction mixture was 1050 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
[ example 11 ]
The catalyst is prepared by mixing and dissolving 101g of zinc acetate (C 4 H 6 O 4 Zn), 0.90g of Ha-containing ammonium fluorohafnate ((NH 4) 2 HaF 6), 0.90g of Zr-containing ammonium fluorozirconate ((NH 4) 2 ZrF 6), 0.60g of Co-containing cobalt acetate (C 4 H 6 CoO 4) and 0.30g of Ni-containing nickel acetate (C 4 H 6 NiO 4) in an aqueous acetic acid solution sufficiently to obtain 350ml of an impregnation solution with pH of 4.8, impregnating 1L of a columnar active carbon carrier of 3mm diameter and 2cm length having a pore volume of 0.80cm 3/g and a specific surface area of 1200m 2/g in the impregnation solution, and standing for 3H at 110 ℃ for drying to obtain the catalyst, wherein the catalyst has a zinc acetate content of 101g/L, a Ha content of 0.90g/L, a Zr content of 0.90g/L, a Co content of 0.60g/L and a Ni content of 0.30 g/L.
The synthesis of vinyl acetate comprises the steps of filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially cutting in acetylene and starting a acetic acid pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 0.20atm, the volume space velocity of raw materials to be 300h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping the reaction after continuously reacting for 50 h.
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 space time yield of vinyl acetate was 76.4 g/(L.h) and the benzene content in the reaction mixture was 420 ppbw. For ease of illustration and comparison, the catalyst composition, the vinyl acetate space time yield of the catalyst, and the benzene content of the reaction mixture are shown in Table 1.
As can be seen from the comparison of comparative example 1 with examples 1 to 11, the group IVB element or the iron-based metal element has the effect of reducing the content of benzene as an impurity in the reaction mixture.
As can be seen by comparing example 7 with examples 1 and 3, Ha and Co have a synergistic effect in reducing the level of benzene as an impurity in the reaction mixture. As can be seen by comparing example 8 with examples 1 and 4, Ha and Ni have a synergistic effect in reducing the content of benzene as an impurity in the reaction mixture. However, comparison of comparative example 5 with examples 3 and 6, or comparison of comparative example 6 with examples 4 and 6 shows that there is no synergistic effect of Zr with Co, or Zr with Ni, in reducing the content of benzene as an impurity in the reaction mixture.
Example 9 in comparison to examples 7 and 8 shows that Co and Ni have a synergistic effect in reducing the level of benzene as an impurity in the reaction mixture.
As can be seen from example 11 in comparison with examples 9 and 10, Ha and Zr have a synergistic effect in reducing the level of benzene as an impurity in the reaction mixture.
TABLE 1

Claims (5)

1. A vinyl acetate synthesis method, taking acetic acid, acetylene as raw materials, synthesizing vinyl acetate under the catalyst for vinyl acetate production, the said catalyst uses active carbon as carrier, the active component includes zinc acetate, and cocatalyst, the said cocatalyst is made up of at least one metal element in hafnium, zirconium and cobalt, nickel; wherein, the content of zinc acetate in the catalyst is as follows: 50-300 g/L, and the content of the cocatalyst is as follows: 0.45-7.50 g/L.
2. The method of synthesizing as claimed in claim 1 wherein the activated carbon is at least one of coal activated carbon, coconut shell activated carbon, apricot shell activated carbon and bamboo activated carbon.
3. The synthesis method according to claim 1, wherein the specific surface area of the activated carbon is 1000 to 1500m 2/g, and the adsorption pore volume is 0.50 to 1.00cm 3/g.
4. The synthesis method according to claim 1, wherein the raw material composition comprises, in terms of mole ratio, acetylene and acetic acid ═ 1 (5-12).
5. The synthesis process according to claim 1, characterized in that the catalyst is prepared by a process comprising the following steps:
Mixing zinc acetate and a solution of a cocatalyst with a carrier according to the composition of a catalyst;
Drying.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4056563A (en) * 1975-01-31 1977-11-01 Boyadzhian Varazdat Karapetovi Method of producing allylacetate
CN105498778A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 Acetylene process vinyl acetate catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4056563A (en) * 1975-01-31 1977-11-01 Boyadzhian Varazdat Karapetovi Method of producing allylacetate
CN105498778A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 Acetylene process vinyl acetate catalyst

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