CN103962179B - Catalyst for acetylene method vinyl acetate synthesis - Google Patents
Catalyst for acetylene method vinyl acetate synthesis Download PDFInfo
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Abstract
The present invention relates to the catalyst for acetylene method vinyl acetate synthesis, the problem that mainly present in solution prior art, catalyst activity is low.The present invention is by using the catalyst for acetylene method vinyl acetate synthesis, including following component: absorbent charcoal carrier, zinc acetate, diether, aromatic esters；Wherein in catalyst, zinc acetate content is the technical scheme of 60 ~ 180 g/L, preferably solves this problem, can be used in the commercial production of acetylene method vinyl acetate synthesis.
Description
Technical field
The present invention relates to the preparation method of the catalyst for acetylene method vinyl acetate synthesis, this catalyst, and the synthetic method of vinyl acetate.
Background technology
Synthesizing Vinyl Acetate from Acetylene refers to react generation vinyl acetate with acetylene and acetic acid under zinc acetate catalyst effect for raw material.Nineteen twenty-two Germany Wacker, company was first by the method for acetylene in gas phase synthesis VAM, improves by Hochst company and puts into commercial production.Its catalyst is with zinc acetate as active component, with activated carbon as carrier, and uses till today always.This catalyst shortcoming includes that activity decrease is fast, and production capacity is the highest, increases along with reaction temperature raises by-product, and catalyst is the longest for service life.Meanwhile, it is simple that acetylene method has technology, and catalyst is inexpensive, be easy to get, and activity is fair, and selectivity is high, the advantages such as expense is low of founding the factory.Therefore, how to be effectively improved the activity of this catalyst and become one important scientific issues of this catalytic field service life, various countries' research worker is started with in terms of active component, promoter, the selection of carrier and modification, catalyst preparation process etc. and this problem has been carried out systematic study, achieves certain phasic results.Acetylene method synthetic route used catalyst active component is mainly zinc acetate, but research worker attempts using other multiple composite oxides to replace zinc acetate as active component.As Japanese scholars proposes with bi component oxide (V2O5-ZnO、Fe2O3-ZnO) or three component oxide (16ZnO 32Fe2O3·V2O5And 24ZnO 8Cr2O3·V2O5) as the active component of catalyst, although above-mentioned catalyst has higher than Zn (OAc) at 250 DEG C2The activity of/C catalyst, but because the shortcomings such as reaction temperature is high, cost is high, activity decrease is fast fail to realize industrialization.Soviet Union scholar once studied the catalyst such as silicate and the 23K-S of Cd and Zn.Chinese patent (CN86107833A, a kind of catalyst for vinyl acetate synthesis and preparation method thereof) reports ZnO-ZnCl2Its space time yield of/C catalyst is higher than Zn (OAc)2/ C catalyst about 30%, but because employing nitrate in this catalyst preparation process, during decomposition, produce a large amount of NOxAnd pollute environment, and catalyst adds ZnCl2, Cl-Equipment is produced corrosivity, limits the popularization of this catalyst.The research substituted for acetylene method vinyl acetate catalyst active component does not make substantial progress, and up to the present, acetylene method vinyl acetate catalyst is still with zinc acetate as active component.Meanwhile, research worker is attempted at Zn (OAc)2/ C catalyst adds promoter and reaches to improve the purpose of catalyst performance.As Chinese patent (CN1903435A, a kind of catalyst for vinyl acetate synthesis and preparation method thereof) selects bismuth subcarbonate as promoter so that the space-time yield of this catalyst has 2.02t/m3D brings up to 2.67t/m3D, catalyst activity improves 32.2%.Master's thesis (University of Fuzhou, 2006, the research of acetylene method vapor-phase synthesis vinyl acetate catalyst) point out that promoter potassium, barium and lanthanum can improve Zn (OAc)2The activity of/C catalyst.The interpolation of promoter significantly improves the activity of this catalyst, and current bismuth subcarbonate has been applied in the production of industrial acetic acid catalyst for ethylene as promoter.
For a long time, both at home and abroad many scholars attempt to replace the experiment of absorbent charcoal carriers unsuccessful with silica gel, aluminium oxide, aluminium silicate and molecular sieve etc..Document (chemistry work, 1962,85 (16): 1；Petrochemical industry, 1979, (8) 7:49) research find, when silica gel, aluminium oxide, aluminium silicate and molecular sieve etc. are as carrier, catalyst activity specific activity high-area carbon catalyst activity is much lower.It was verified that activated carbon is as acetylene method vinyl acetate catalyst carrier, up to the present can not be substituted.Meanwhile, research worker considers to modify absorbent charcoal carrier, thus reaches to improve the purpose of carrier property.As document (petrochemical industry, 2004,33 (11): 1024) research finds, the activated carbon crossed through mass fraction 15% nitric acid treatment is that the catalyst that carrier prepares improves 5.36% than the activity that undressed activated carbon is the catalyst that carrier prepares.Chinese patent (CN102029193A, a kind of activated carbon making catalyst carrier and processing method thereof and application) select hydrogen peroxide that absorbent charcoal carrier is carried out pre-treatment, result shows, uses the described method of this invention to process its catalysis activity raising 2 ~ 15% of catalyst that the activated carbon obtained prepares.Chinese patent (CN102284304A, a kind of preparation method of high-efficiency catalyst for vinyl acetate synthesis by acetylene method) in addition to hydrogen peroxide, also select a series of oxidants such as sulphuric acid, potassium permanganate and Ammonium persulfate. that activated carbon carries out after pre-treatment the preparation for catalyzer for synthesizing vinyl acetate, this patent only reports the percentage composition of vinyl acetate in product, the activity data of this catalyst undeclared.Though selecting oxidant that absorbent charcoal carrier carries out pre-treatment can improve the activity of catalyst to a certain extent, but the activated carbon after acid or other oxidizer treatment mostly need to through long-time washing, extract that to make activated carbon be neutrality, and drying time is long, add production time and the cost of catalyst.
It addition, some investigators uses other derived carbon to replace coal mass active carbon as the carrier of vinyl acetate catalyst recently.Such as Chinese patent (CN101402052A, the catalyst of producing vinyl acetate by acetylene method technique and preparation method) select papermaking lignin by acid separation be that absorbent charcoal carrier prepared by raw material, make vinyl acetate catalyst after load zinc acetate, the reaction prepare vinyl acetate has good activity.And Chinese patent (CN101439302A, the catalyst of producing vinyl acetate by acetylene method and preparation method and the application of catalyst) select resin base derived carbon, the Vingon microsphere i.e. prepared with suspension polymerization is as precursor, or the polyvinylidene chloride resin directly through mechanical pelleting, polyvinylidene chloride resin being formed required molding granularity is precursor, through carbonization, washs, be dried to obtain catalyst carrier.Vinyl acetate catalyst is obtained through load zinc acetate active component.It is good that the catalyst using the method to prepare has mechanical strength, compound with regular structure, it is easy to filling, and demonstrates good catalytic performance.Additionally, Chinese patent (CN101385984A, catalyst of producing vinyl acetate by acetylene method and preparation method thereof and purposes) selects the precursor resin microsphere derived carbon that to be acrylonitrile obtain with vinylidene chloride copolymerization to be carrier, load zinc acetate and prepare vinyl acetate catalyst.The derived carbon carrier of above-mentioned patent report has certain Research Prospects.But the activity of catalyst has much room for improvement in prior art.
Summary of the invention
One of the technical problem to be solved is the problem that catalyst activity is low present in prior art, it is provided that a kind of new vinyl acetate catalyst, the active high feature of this catalyst.
The two of the technical problem to be solved, are to provide the preparation method of one of a kind of and above-mentioned technical problem corresponding catalyst.
The three of the technical problem to be solved, are to provide the synthetic method of a kind of vinyl acetate using the described catalyst of one of above-mentioned technical problem.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: for the catalyst of acetylene method vinyl acetate synthesis, including following component: absorbent charcoal carrier, zinc acetate, diether, aromatic esters；Wherein in catalyst, zinc acetate content is 60 ~ 180g/L.
Described in technique scheme, in catalyst, diether and aromatic esters total content are preferably 2.0 ~ 10g/L；Described diether is preferably at least one in alkyl diether, more preferably diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol ethylmethyl ether；Described aromatic esters are preferably ortho position aromatic diesters；Described ortho position aromatic diesters is more preferably at least one in dimethyl phthalate, diethyl phthalate or phthalic acid methyl ethyl ester；The most described alkyl diether is preferably 1:0.2 ~ 5.0 with the ratio of ortho position aromatic diesters；Described activated carbon is preferably ature of coal column charcoal, and specific surface area is 1000 ~ 1300cm2/ g, adsorbing total pore volume is 0.6 ~ 0.8cm3/g。
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of catalyst as described above, comprises the following steps:
The preparation of (a) impregnation liquid: the desired amount of zinc acetate, diether being dissolved in solvent with aromatic esters and make impregnation liquid, described solvent consists of by weight percentage: methanol 80 ~ 100wt%, water 0 ~ 20wt%；
The dipping of (b) carrier: the desired amount of carrier is mixed with above-mentioned impregnation liquid；
C () is dried to obtain catalyst.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: the method for vinyl acetate synthesis, in the presence of catalyst described in one of technical problem any one technical scheme, acetylene is consisted of: acetic acid=5 ~ 12:1 with molar ratio computing raw material, reaction pressure is 0.1 ~ 0.5atm, reaction temperature is 160 ~ 220 DEG C, and raw material volume air speed is 250 ~ 350h-1。
Reaction pressure of the present invention is gauge pressure.
Select with prior art compared with zinc acetate load type active carbon prepares vinyl acetate catalyst, present invention adds the diether mixture with aromatic esters as promoter, interact with zinc acetate and absorbent charcoal carrier and play the better effects improving catalyst activity.Further, the present invention selects alkyl diether and ortho position aromatic diesters mixture as promoter, has synergism at the active aspect that improve catalyst.Test result indicate that, the space-time yield of catalyst of the present invention is 3.36t/m3D, catalyst activity current commercial Application Zn (OAc) on year-on-year basis2/ C catalyst improves 50.7%, achieves preferable technique effect.
Detailed description of the invention
[embodiment 1]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.45g diethylene glycol dimethyl ether, 0.45g dimethyl phthalate and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and diether and aromatic esters total content are 5.0g/L；
The dipping of (a) carrier: selected activated carbon is the cylindric charcoal of ature of coal (diameter 2.4mm, long 2cm), and specific surface area is 1200cm2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
B () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
(2) physical property characterizes
Use inductively coupled plasma spectrogrph (ICP) to measure Zn content in catalyst, impregnate diether and the total content of aromatic esters in before and after's impregnation liquid by liquid chromatograph, thus obtain diether and aromatic esters total content in catalyst.The preparation condition of catalyst is listed in table 1.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 30ml；
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=6:1；
Reaction raw materials volume space velocity: 300h-1；
Reaction pressure: 0.3atm；
Reaction temperature: 180 DEG C；
Response time: 100h.
Reaction 100h, with the content of each component in gas chromatography analytical reactions product, calculates the space-time yield of this catalyst.For ease of comparing, essential condition is listed in table 2.
[embodiment 2] to [embodiment 5]
Except changing in catalyst preparation process in addition to the kind of promoter diether and aromatic esters, other operating procedure and appreciation condition are the most same as in Example 1.For ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterize evaluation result and be listed in table 2.
[embodiment 6]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.75g diethylene glycol dimethyl ether, 0.15g diethyl phthalate and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and diether and aromatic esters total content are 5.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
Catalyst physical property characterizes same as in Example 1, and evaluating catalyst uses fixed-bed catalysts evaluating apparatus same as in Example 1 and appreciation condition, for ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterizes evaluation result and is listed in table 2.
[embodiment 7]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.15g diethylene glycol dimethyl ether, 0.75g diethyl phthalate and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and diether and aromatic esters total content are 5.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
Catalyst physical property characterizes same as in Example 1, and evaluating catalyst uses fixed-bed catalysts evaluating apparatus same as in Example 1 and appreciation condition, for ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterizes evaluation result and is listed in table 2.
[embodiment 8]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.18g diethylene glycol dimethyl ether, 0.18g diethyl phthalate and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and diether and aromatic esters total content are 2.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
(2) physical property characterizes
Use inductively coupled plasma spectrogrph (ICP) to measure Zn content in catalyst, impregnate diether and aromatic esters total content in before and after's impregnation liquid by liquid chromatograph, thus obtain diether and aromatic esters total content in catalyst.The preparation condition of catalyst is listed in table 1.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 30ml；
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=5:1；
Reaction raw materials volume space velocity: 250h-1；
Reaction pressure: 0.1atm；
Reaction temperature: 160 DEG C；
Response time: 100h.
Reaction 100h, with the content of each component in gas chromatography analytical reactions product, calculates the space-time yield of this catalyst.For ease of comparing, essential condition is listed in table 2.
[embodiment 9]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.90g diethylene glycol dimethyl ether, 0.90g diethyl phthalate and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and diether and aromatic esters total content are 10.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
(2) physical property characterizes
Use inductively coupled plasma spectrogrph (ICP) to measure Zn content in catalyst, impregnate diether and the total content of aromatic esters in before and after's impregnation liquid by liquid chromatograph, thus obtain diether and aromatic esters total content in catalyst.The preparation condition of catalyst is listed in table 1.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 30ml；
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=8:1；
Reaction raw materials volume space velocity: 250h-1；
Reaction pressure: 0.2atm；
Reaction temperature: 170 DEG C；
Response time: 100h.
Reaction 100h, with the content of each component in gas chromatography analytical reactions product, calculates the space-time yield of this catalyst.For ease of comparing, essential condition is listed in table 2.
[embodiment 10]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.45g diethylene glycol dimethyl ether, 0.45g diethyl phthalate and 9.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 80wt% by weight percentage, water 20wt%) in water mixed solvent2Content is 50g/L, and diether and aromatic esters total content are 5.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
(2) physical property characterizes
Use inductively coupled plasma spectrogrph (ICP) to measure Zn content in catalyst, impregnate diether and the total content of aromatic esters in before and after's impregnation liquid by liquid chromatograph, thus obtain diether and aromatic esters total content in catalyst.The preparation condition of catalyst is listed in table 1.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 30ml；
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=10:1；
Reaction raw materials volume space velocity: 350h-1；
Reaction pressure: 0.4atm；
Reaction temperature: 200 DEG C；
Response time: 100h.
Reaction 100h, with the content of each component in gas chromatography analytical reactions product, calculates the space-time yield of this catalyst.For ease of comparing, essential condition is listed in table 2.
[embodiment 11]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.45g diethylene glycol dimethyl ether, 0.45g diethyl phthalate and 27.0gZn (OAc)2It is dissolved in methanol solvate under the conditions of 50 DEG C and makes 180ml impregnation liquid, wherein Zn (OAc)2Content is 150g/L, and diether and aromatic esters total content are 5.0g/L；
The dipping of (b) carrier: selected activated carbon is that (diameter 2.4mm, long 2cm, specific surface area is 1200cm to the cylindric charcoal of ature of coal2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
(2) physical property characterizes
Use inductively coupled plasma spectrogrph (ICP) to measure Zn content in catalyst, impregnate diether and the total content of aromatic esters in before and after's impregnation liquid by liquid chromatograph, thus obtain diether and aromatic esters total content in catalyst.The preparation condition of catalyst is listed in table 1.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 30ml；
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=12:1；
Reaction raw materials volume space velocity: 350h-1；
Reaction pressure: 0.5atm；
Reaction temperature: 220 DEG C；
Response time: 100h.
Reaction 100h, with the content of each component in gas chromatography analytical reactions product, calculates the space-time yield of this catalyst.For ease of comparing, essential condition is listed in table 2.
[embodiment 12]
Except changing in catalyst preparation process in addition to promoter kind and ratio, other operating procedure and appreciation condition are the most same as in Example 1.For ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterize evaluation result and be listed in table 2.
[comparative example 1]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 0.9g diethylene glycol dimethyl ether and 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L, and two ether contents are 5.0g/L；
The dipping of (b) carrier: selected activated carbon is the cylindric charcoal of ature of coal (diameter 2.4mm, long 2cm), and specific surface area is 1200cm2/ g, adsorbing total pore volume is 0.7cm3/g；This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
Catalyst physical property characterizes same as in Example 1, and evaluating catalyst uses fixed-bed catalysts evaluating apparatus same as in Example 1 and appreciation condition, for ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterizes evaluation result and is listed in table 2.
[comparative example 2] to [comparative example 4]
Except changing in catalyst preparation process in addition to promoter kind and ratio, other operating procedure and appreciation condition are all identical with comparative example 1.For ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterize evaluation result and be listed in table 2.
[comparative example 5]
(1) prepared by catalyst
The preparation of (a) impregnation liquid: by 18.0gZn (OAc)2Under the conditions of 50 DEG C, it is dissolved in methanol makes 180ml impregnation liquid, wherein Zn (OAc) with (methanol 90wt% by weight percentage, water 10wt%) in water mixed solvent2Content is 100g/L；
The dipping of (b) carrier: selected activated carbon is the cylindric charcoal of ature of coal (a diameter of 2.4mm, long 2cm), and specific surface area is 1200cm2/ g, adsorbing total pore volume is 0.7cm3/g.This absorbent charcoal carrier of 100ml is joined in above-mentioned impregnation liquid, carries out impregnating 4h under the conditions of 70 DEG C, filter；
C () is dried: being dried 6h under the conditions of 105 DEG C and obtain catalyst, gained catalyst can carry out catalyst performance evaluation after loading reactor.
Catalyst physical property characterizes same as in Example 1, and evaluating catalyst uses fixed-bed catalysts evaluating apparatus same as in Example 1 and appreciation condition, for ease of comparing, catalyst preparation conditions is listed in table 1, evaluating catalyst condition, characterizes evaluation result and is listed in table 2.
Table 1 catalyst preparation conditions
| Zinc acetate content in impregnation liquid, g/L | Diether and aromatic esters total content, g/L in impregnation liquid | Promoter kind and weight ratio | Solvent species and percentage composition (wt%) | |
| Embodiment 1 | 100 | 5.0 | Diethylene glycol dimethyl ether: dimethyl phthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 2 | 100 | 5.0 | Diethylene glycol dimethyl ether: phthalic acid methyl ethyl ester=1:1 | Methanol/water: 90/10 |
| Embodiment 3 | 100 | 5.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 4 | 100 | 5.0 | Diethylene glycol dimethyl ether: dimethyl isophthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 5 | 100 | 5.0 | Diethylene glycol dimethyl ether: diethyl terephthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 6 | 100 | 5.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:0.2 | Methanol/water: 90/10 |
| Embodiment 7 | 100 | 5.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:5 | Methanol/water: 90/10 |
| Embodiment 8 | 100 | 2.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 9 | 100 | 10.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:1 | Methanol/water: 90/10 |
| Embodiment 10 | 50 | 5.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:1 | Methanol/water: 80/20 |
| Embodiment 11 | 150 | 5.0 | Diethylene glycol dimethyl ether: diethyl phthalate=1:1 | Methanol: 100 |
| Embodiment 12 | 100 | 5.0 | Diethylene glycol dimethyl ether: ethyl benzoate=1:1 | Methanol/water: 90/10 |
| Comparative example 1 | 100 | 5.0 | Diethylene glycol dimethyl ether | Methanol/water: 90/10 |
| Comparative example 2 | 100 | 5.0 | Diethyl phthalate | Methanol/water: 90/10 |
| Comparative example 3 | 100 | 5.0 | Dimethyl isophthalate | Methanol/water: 90/10 |
| Comparative example 4 | 100 | 5.0 | Diethyl terephthalate | Methanol/water: 90/10 |
| Comparative example 5 | 100 | 5.0 | --- | Methanol/water: 90/10 |
Table 2(is continued) catalyst characterization and appreciation condition data
| Active component content (g/L) in catalyst | Cocatalyst content (diether and aromatic esters total content, g/L) in catalyst | Reaction pressure (atm) | |
| Embodiment 1 | 120 | 5.0 | 0.3 |
| Embodiment 2 | 120 | 5.0 | 0.3 |
| Embodiment 3 | 120 | 5.0 | 0.3 |
| Embodiment 4 | 120 | 5.0 | 0.3 |
| Embodiment 5 | 120 | 5.0 | 0.3 |
| Embodiment 6 | 120 | 5.0 | 0.3 |
| Embodiment 7 | 120 | 5.0 | 0.3 |
| Embodiment 8 | 120 | 2.0 | 0.1 |
| Embodiment 9 | 120 | 10.0 | 0.2 |
| Embodiment 10 | 60 | 5.0 | 0.4 |
| Embodiment 11 | 180 | 5.0 | 0.5 |
| Embodiment 12 | 120 | 5.0 | 0.3 |
| Comparative example 1 | 120 | 5.0 | 0.3 |
| Comparative example 2 | 120 | 5.0 | 0.3 |
| Comparative example 3 | 120 | 5.0 | 0.3 |
| Comparative example 4 | 120 | 5.0 | 0.3 |
| Comparative example 5 | 120 | --- | 0.3 |
Table 2(continues) catalyst characterization and appreciation condition data
| Reaction temperature (DEG C) | Volume space velocity (h-1) | Material molar ratio (acetylene: acetic acid) | Space-time yield (t/m3·d) 8 --> | |
| Embodiment 1 | 180 | 300 | 6:1 | 3.12 |
| Embodiment 2 | 180 | 300 | 6:1 | 3.20 |
| Embodiment 3 | 180 | 300 | 6:1 | 3.36 |
| Embodiment 4 | 180 | 300 | 6:1 | 3.21 |
| Embodiment 5 | 180 | 300 | 6:1 | 3.01 |
| Embodiment 6 | 180 | 300 | 6:1 | 3.18 |
| Embodiment 7 | 180 | 300 | 6:1 | 3.21 |
| Embodiment 8 | 160 | 250 | 5:1 | 2.88 |
| Embodiment 9 | 170 | 250 | 8:1 | 2.13 |
| Embodiment 10 | 200 | 350 | 10:1 | 1.62 |
| Embodiment 11 | 220 | 350 | 12:1 | 1.41 |
| Embodiment 12 | 180 | 300 | 6:1 | 3.01 |
| Comparative example 1 | 180 | 300 | 6:1 | 2.58 |
| Comparative example 2 | 180 | 300 | 6:1 | 2.65 |
| Comparative example 3 | 180 | 300 | 6:1 | 2.36 |
| Comparative example 4 | 180 | 300 | 6:1 | 2.40 |
| Comparative example 5 | 180 | 300 | 6:1 | 2.23 |
Claims (4)
1. for the catalyst of acetylene method vinyl acetate synthesis, including following component: absorbent charcoal carrier, zinc acetate, alkyl ether, aromatic esters；
Wherein, in catalyst, zinc acetate content is 60-180g/L；Described alkyl ether and aromatic esters total content are 2.0～10g/L；Described alkyl ether is at least one in diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol ethylmethyl ether；Described aromatic esters are ortho position aromatic diesters；Described activated carbon is ature of coal column charcoal, and specific surface area is 1000～1300cm2/ g, adsorbing total pore volume is 0.6～0.8cm3/g；The most described alkyl ether is 1:0.2～5.0 with the ratio of ortho position aromatic diesters.
2. catalyst as claimed in claim 1, it is characterised in that described ortho position aromatic diesters is at least one in dimethyl phthalate, diethyl phthalate or phthalic acid methyl ethyl ester.
3. the preparation method of catalyst described in any one of claim 1～2, comprises the following steps:
The preparation of (a) impregnation liquid: the desired amount of zinc acetate, alkyl ether being dissolved in solvent with aromatic esters and make impregnation liquid, described solvent consists of by weight percentage: methanol 80～100wt%, water 0～20wt%；
The dipping of (b) carrier: the desired amount of carrier is mixed with above-mentioned impregnation liquid；
C () is dried to obtain catalyst.
4. the method for vinyl acetate synthesis, in the presence of catalyst as according to any one of claim 1～2, consisting of acetylene with molar ratio computing raw material: acetic acid=5～12:1, reaction pressure is 0.1～0.5atm, reaction temperature is 160～220 DEG C, and raw material volume air speed is 250～350h-1。
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| Method of preparation of an activated carbon supported zinc acetate catalyst;Toshio Kawaguchi, et al.;《Applied Catalysis》;19871231;第32卷;第23-36页 * |
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