CN86107833A - Zinc oxide catalytic agent for synthesizing of acetic acid ethylene - Google Patents
Zinc oxide catalytic agent for synthesizing of acetic acid ethylene Download PDFInfo
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Abstract
The present invention is preparation and the application that belongs to acetylene method fluid bed catalyzer for synthesizing vinyl acetate.Zinc nitrate and zinc chloride bi-component are loaded on the higher carrier active carbon of intensity, and zinc oxide is cocatalyst component for the major catalyst zinc chloride.Make Zinc oxide catalytic through roasting.Component of this catalyst and method for making thereof are investigated the result with pool, palace three youth's result of study differences of Japan 1000 tons of/year synthesizing vinyl acetate pilot scales, and space time yield can improve about 30%.The best proportioning of Zinc oxide catalytic is an active carbon: zinc oxide: zinc chloride=100: 23: 4.3 (weight).
Description
The present invention belongs to the preparation of acetylene method fluid bed catalyzer for synthesizing vinyl acetate and the technical field of application.
Aspect the production of acetylene method synthesizing vinyl acetate, the main both at home and abroad attached zinc acetate catalyst of carried by active carbon (hereinafter to be referred as zinc acetate catalyst) that adopts.The present invention is to be carrier with the active carbon, zinc oxide is the main catalytic component, zinc chloride is the zinc oxide～zinc chloride～activated-carbon catalyst (hereinafter to be referred as Zinc oxide catalytic) that helps catalyst component to form, be used for the acetylene method synthesizing vinyl acetate and obtained with zinc acetate catalyst and compare, more positive effect is arranged.
Acetylene gas is combined to the industrial catalyst of vinyl acetate, still uses the attached zinc acetate catalyst of carried by active carbon so far.This uses charcoal to carry attached zinc acetate catalyst since nineteen twenty-two Mugdan, and much research afterwards replaces charcoal to do carrier with active carbon, and almost as the carrier of unique industrial catalyst, monopolizes for a long time.
(in " first volume of the synthesizing vinyl acetate catalyst carrier technical data " 55～71(1976), introducing Korea and adopting sawdust charcoal to carry attached zinc acetate catalyst; Japan adopts the coconut husk charcoal to carry attached acetate catalyst.
The domestic attached zinc acetate catalyst of various shell class carried by active carbon that now still adopts based on the coconut husk charcoal; Polyvinyl factory in Sichuan adopts the coal charcoal processing to carry attached zinc acetate and basic bismuth carbonate (co-catalyst) catalyst only, is used for fixing in the production of a synthesizing vinyl acetate.
At (122(1971 of Beijing Organic Chemical Plant " technological innovation compiles ")) in, narration silica gel carries attached zinc oxide, aluminium oxide and zinc chloride catalyst, last big twice pilot production situation, main existing problems are that reactant liquor is of poor quality, fatal weakness such as catalyst has coking phenomenon, and the sticking support strength of silicon is not enough.
(Gu Zhaofu " Japanese The Chemicals " V81 № 2298(1960)) in point out: independent zinc acetate or independent active carbon, chemisorption is not taken place in acetylene, to synthesizing vinyl acetate yet catalytically inactive.Active carbon Dichlorodiphenyl Acetate zinc not only provides surface area but also has activation energy with the zinc acetate chemical bond.
Except that zinc acetate, the acetate of cadmium, mercury and bismuth is loaded on the active carbon, and the reaction by acetylene and acetic acid synthesizing vinyl acetate is all had catalytic action, but less and cheap and easy to get because of the toxicity of zinc, is widely adopted industrial.
But the used zinc acetate catalyst of synthesizing vinyl acetate has following weakness at present:
(1) loss of zinc acetate distillation at high temperature is big, and very fast decay is active.
(2) thermal decomposition of zinc acetate generation at high temperature produces carbon deposit and pollutes catalyst surface, thereby has a strong impact on catalytic activity and life-span.
(3) space time yield is not high during zinc acetate catalyst, only is 1.0～1.2 kilograms/liter day will improve the acetic acid conversion ratio, should improve reaction temperature, but improves temperature, then the impurity disliked such as the high as crotonaldehyde of impurity content.
Palace pool three youths have systematically explored the oxidized metal catalyst according to the problems referred to above from 1958, and discovery compares with existing catalyst, have the outstanding catalyst (pool, palace three youths " industrial chemistry magazine " V61 № 5614(1958) of several times activity).But it gets from the little test result of fixed bed, does not see the industrialization report so far as yet.The catalyst of pool, palace three youths research exists following problem:
(1) adopts the coprecipitation preformed catalyst, be difficult to proof strength, not necessarily be applicable to the fluid bed synthesizing vinyl acetate.
(2) catalytic component is more and the metal oxide consumption is bigger, as the oxidized metal catalyst: composite catalyst A:3ZnOCr and for example
2O
3+ C, composite catalyst B:3ZnOCr
2O
3+ C+ZnCl
2Deng
(3) catalyst preparation process is complicated, i.e. co-precipitation, filtration, drying, fragmentation are sieved and roasting etc., need time-consuming again through multiple operation.
At above problem, what we developed is to simplify working process, and reduces active component, can be applicable to the fluid bed catalyzer for synthesizing vinyl acetate.We adopt zinc nitrate and zinc chloride bi-component to be loaded on the higher carrier active carbon of milling intensity, and drying makes Zinc oxide catalytic through roasting again, and its component and method for making thereof are with pool, palace three youth's result of study differences.The Zinc oxide catalytic of our development is on 1000 tons of/year pilot-plants, and synthesizing vinyl acetate is investigated the result, and space time yield can improve about 30%.
Fujian Province international online retrieval service department utilizes No. 399 documents (U.S. chemical abstract) in the U.S. DIALOG database to retrieve in 1963 to 1966 on March 18th, 1986; The document of relevant " vinyl acetate zinc oxide～zinc chloride new catalyst " problem, result for retrieval are zero.
Purpose of the present invention: we think not only with carrier active carbon but also select for use the catalyst of active component to be advisable.Select zinc nitrate for use, the zinc chloride bi-component is carried on the attached active carbon, and satisfied substantially through the Zinc oxide catalytic that roasting makes, component is few, proportioning is simple, especially should select for use and can suppress zinc acetate distillation and the component of decomposing, raw material is cheap and easy to get, and catalyst preparation process is simple, economical rationality, active high, the life-span is long, guarantees the quality of reactant liquor.
Analyze according to us, the metal oxide catalyst of pool, palace three youths development is compared with existing zinc acetate catalyst, and is strong active high, but there are the following problems:
(1), the catalyst that only adopts the co-precipitation moulding to make without carrier, be difficult to proof strength, be not suitable for fluidized bed process.
(2), pool, palace three youths also reported the catalyst of metal oxide with the active carbon combination, but reported how active component is not downloaded on the active carbon.
We think not only with carrier active carbon but also select for use the catalyst of active component to be advisable.Adopt carrier that following benefit is arranged:
(1), carrier active carbon not only provides surface area but also has active site with the active component chemical bond active component.
(2), can guarantee the mechanical strength of catalyst to be applicable to the operation of fluid bed.
(3), save active component, economical rationality.
But the employing carrier active carbon is not optional but will satisfies following condition:
(1), bigger surface area activated carbon can be provided, as more long-pending than table be about 1100～1350 meters squared per gram, average pore size is 20
About and evenly flourishing micropore.
(2), active carbon with certain mechanical strength, be about 70% carrier active carbon as milling intensity.
We have adopted almond and coconut husk carrier active carbon.Because this shell carrier active carbon meets above-mentioned condition and on producing, long-tested good carrier.
The present invention selects for use active component also will satisfy following requirement:
(1), component is few, proportioning is simple.Especially should select for use and can suppress zinc acetate distillation and the component of decomposing.
(2), raw material is cheap and easy to get.
(3), catalyst preparation process is simple, economical rationality.
(4), the activity of such catalysts height, the quality that the life-span is long, guarantee reactant liquor.
(5), in preparation catalyst process, for the waste gas that produces control measures is arranged.
Existing zinc acetate catalyst has following weakness:
(1), zinc acetate distillation loss under the high temperature, make the catalytic activity decay very fast.
(2), high warm zinc acetate generation thermal decomposition down, produce carbon deposit and pollute catalyst surface and have a strong impact on catalytic activity and life-span.
(3), to improve acetic acid conversion ratio and space time yield, must improve reaction temperature.One temperature raising just increases matter matter content such as crotonaldehyde, influences the quality of reactant liquor.
Zinc oxide catalytic of the present invention has overcome the weakness of zinc acetate catalyst.When Zinc oxide catalytic is main component and when depositing a certain amount of zinc chloride with zinc oxide, partial oxidation zinc forms zinc acetate with acetic acid in the initial stage and process of synthetic reaction.Zinc acetate has formed Zn(OAC again with zinc chloride)
2ZnCl
2Molecular compound.This molecular compound forms fused matter with superfluous zinc acetate again.Thereby the vapour pressure that makes zinc acetate significantly reduces and obviously reduces the distillation and the thermal decomposition loss of zinc acetate.As the zinc chloride of co-catalyst, the effect of inhibitor has been played in the distillation of Dichlorodiphenyl Acetate zinc and thermal decomposition.Simultaneously the generation of crotonaldehyde has also been played the effect of inhibitor.Because this effect, Zinc oxide catalytic is compared with zinc acetate catalyst, increases substantially catalytic activity and life-saving, guarantees the quality of reactant liquor,
The best proportioning of Zinc oxide catalytic is:
Active carbon: zinc oxide: zinc chloride=100: 23: 4.3(weight)
By the Zinc oxide catalytic of producing on 150 tons of/year pilot-plants, investigate the result by synthesizing vinyl acetate on 1000 tons of/year pilot-plants, reached the purpose of the phase of giving.
Content of the present invention
1, uses raw material
(1) zinc nitrate: purity 98%.
(2) zinc chloride: purity 98%.
(3) active carbon: the coconut husk or the almond carrier active carbon that adopt domestic acetylene method fluid bed catalyzer for synthesizing vinyl acetate to use.
2, catalyst proportion
Active carbon: zinc oxide: zinc chloride=100: 23: 4.3(weight)
3, main technique condition
(1) spray solution temperature: 50～65 ℃
(2) baking temperature: 80～100 ℃
(3) sintering temperature: 250～300 ℃
(4) hot blast linear velocity: 0.2～0.3 meter per second
Advantage
Zinc oxide catalytic is compared with existing zinc acetate catalyst, and advantage is active height, the life-span is long, selectivity good.
1, catalytic activity
With the Zinc oxide catalytic that makes on 30 tons/year and 150 tons of/year pilot-plants, on 1000 tons of/year synthesizing vinyl acetate devices, investigate respectively.
Twice pilot-scale experiment table 1
Fujian polyvinyl factory of factory name Siping City amalgamation factory
Catalyst type zinc acetate zinc oxide zinc acetate zinc acetate zinc oxide
Catalyst internal memory m
37.9 5.5 4.0 4.0 3.97
Reaction temperature ℃ 168-216 175-220 185-200 176-195 190-224
Mole ratio C
2H
2/ HOAC 3.3 2.0-2.5 2.4-2.6 2.4-2.6 2.4-2.6
Air speed hr
-1176 170 140-170 140-170 140-170
Mix acetylene flow Nm
3/ hr 1,106 750 400-450 450 450
Acetic acid evaporation capacity kg/hr 767 800 400-450 430 460-550
Space yield T/m
3D 0.9-1.0 1.3-1.6 1.29 1.35 1.76
By table 1 as seen, Zinc oxide catalytic is compared with zinc acetate catalyst, and space time yield can improve about 30%.
2, catalyst life
In order to investigate catalyst life, Zinc oxide catalytic and existing zinc acetate catalyst with pilot-plant prepares all on the fixed bed synthesizing vinyl acetate device of laboratory, adopt intensified condition separately, are contrasted.
Table 2 explanation Zinc oxide catalytic is compared with zinc acetate catalyst, and active rate of descent obviously reduces.The life-span that promptly shows the former is much longer.
Two kinds of life of catalyst contrast tables 2
Catalyst type zinc acetate catalyst Zinc oxide catalytic
Catalyst loading amount ml 135 135
Reaction temperature ℃ 195 210
Air speed hr
-1170 220
Mole ratio C
2H
2/ HOAC 2.5 1.5
Reaction time hr 99 99.25
Initial activity T/m
3D 3.96 3.96
Latter stage active T/m
3D 2.79 3.19
Active rate of descent % 29.55 19.44
3, synthesis reaction solution quality
Synthesizing vinyl acetate reactant liquor quality quality is an important symbol of weighing a kind of catalyst selectivity quality.Zinc acetate catalyst is in the synthesizing vinyl acetate process, and the past people once wanted to improve reaction temperature and improve the acetic acid softening rate.Yet because the raising of temperature, and the crotonaldehyde content in the synthesis reaction solution obviously increases, at high temperature selectivity is very poor to have shown zinc acetate catalyst.
The quality table 3 of synthesis reaction solution
Catalyst type zinc acetate catalyst Zinc oxide catalytic
Reaction temperature ℃ 176～195 190～224
Acetaldehyde % 1.16 1.06
Crotonaldehyde content % 0.91 0.64
Specific activity △ t 1 ' 50 " 81 ' 44 " 4
By table by table 3 as seen, Zinc oxide catalytic is more much higher than the reaction temperature of zinc acetate catalyst, but the quality of its reactant liquor is good, and particularly crotonaldehyde content is low.The selectivity that has shown Zinc oxide catalytic is better than zinc acetate catalyst.
(7) for example
Example 1: according to the requirement of catalyst proportion, make the consumption of zinc nitrate and zinc chloride,, be made into mixed aqueous solution in the ratio of wiring solution-forming cumulative volume to almond active carbon weight ratio 1.5.In water-bath, be heated to 45 ℃, evenly be sprayed on the almond active carbon, put into 80 ℃ of following dryings of electric dry oven then 2 hours, be warming up to 103 ± 2 ℃ of dryings again 2 hours, regularly stir in the dry run.Dried catalyst is put into the tubular type roaster, and logical nitrogen is warming up to 250 ℃ after 15 minutes, continues under nitrogen constant temperature calcining 5 hours, makes zinc nitrate be decomposed into zinc oxide.Catalyst after the roasting does not have nitrate anion through the qualitative analysis of diphenylamines method.This is called the bi-component roasting method.
The relation table 4 of zinc oxide content and activity and reactant liquor quality
Zinc oxide content air speed mole ratio reaction temperature ℃ space time yield specific activity
28.5 220 1.5 200 2.37 48″9
23.0 220 1.5 200 2.79 49″0
20.0 220 1.5 200 2.72 2′03″8
By table 4 as seen, if zinc chloride content is fixed as the 4.3g/100g charcoal, then zinc oxide content is with 23g/100g charcoal left and right sides optimum, and its space time yield is the highest, and specific activity (referring to the reactant liquor quality) is not bad.
Example 2: the one pack system roasting method be carry earlier go up zinc nitrate after, carry out drying and roasting, and then carry and go up the zinc chloride drying and get final product, except year attached zinc chloride of back, other methods of operating are with example 1.
Bi-component roasting and one pack system roasting contrast table 5
Roasting method bi-component one pack system
Air speed 220 220
Mole ratio 1.5 1.5
Reaction temperature ℃ 210 210
Reaction time 41.5 42
Initial activity T/m
3D 4.06 4.06
Latter stage active T/m
3D 3.91 2.90
Active rate of descent % 3.7 28.6
Specific activity 1,254 1128
By table 5 as seen, the catalyst of bi-component roasting and one pack system roasting, the specific activity of initial activity and reactant liquor is near each other, but active rate of descent is significantly different.The bi-component roasting is than one pack system roasting, and active rate of descent is much smaller, and this explanation has remarkable effect to prolonging catalyst life.
Example 3: on 30 tons of/year pilot-plants that zinc nitrate and zinc chloride is water-soluble, be mixed with 536 grams per liter zinc nitrate solutions and 146 grams per liter liquor zinci chloridis respectively.Then they two are mixed by 1: 0.3 volume ratio, be heated to 45 ℃.Be sprayed on the coal activated carbon by 1.3 bath raioes, drying makes the zinc nitrate roasting become Zinc oxide catalytic with hot-air.
On 1000 tons of/year synthesizing vinyl acetate devices, carried out contrast with existing zinc acetate catalyst and investigated.
Two kinds of catalyst activity contrast tables 6
Catalyst type Zinc oxide catalytic zinc acetate catalyst
Catalyst internal memory m
35.5 7.9
Reaction temperature ℃ 175～220 168～216
Mole ratio C
2H
2/ HOAC 2.0～2.5 3.3
Air speed hr
-1170 176
Space time yield T/m
3D 1.3～1.6 0.9～1.0
Table 6 explanation Zinc oxide catalytic is than zinc acetate catalyst, and space time yield is high more than 30%.
Example 4: on 150 tons of/year pilot-plants, every batch takes by weighing 175 kilograms of zinc nitrates and 8.8 kilograms of zinc chloride are put into dissolution kettle, add 200 liter deionized waters, after heating for dissolving finishes while stirring, again deionized water is added to 300 liters, when being heated to 50～65 ℃, evenly be sprayed on the coal activated carbon by 1.5 bath raioes, carry out drying then, make material contain warm rate and reach till 20～25%, under 250 ℃, carry out 3 hours constant temperature calcinings again, make Zinc oxide catalytic.
Urge agent synthesising reacting process condition and table 7 as a result thereof for two kinds
Catalyst type zinc acetate catalyst Zinc oxide catalytic
Catalyst internal memory m
34.0 3.97
Reaction temperature ℃ 176～195 190～224
Mole ratio 2.4～2.6 2.4～2.6
Air speed 140～170 140～170
Acetaldehyde % 1.16 1.06
Crotonaldehyde content % 0.91 0.636
Specific activity 1,508 1444
Space time yield T/m
3D 1.35 1.76
On 1000 tons of/year synthesizing vinyl acetate devices, having carried out contrast with existing zinc acetate catalyst, to investigate the result as shown in table 7, Zinc oxide catalytic be described than zinc acetate catalyst, and space time yield is high by 30%, selectivity.
Claims (5)
1, the preparation Zinc oxide catalytic agent for synthesizing of acetic acid ethylene is characterized in that using attached zinc nitrate of carried by active carbon and zinc chloride.
2, by right 1 described preparation Zinc oxide catalytic, the raw material that it is characterized in that using requires certain purity as zinc nitrate and zinc chloride, and its active carbon is coconut husk, the almond that adopts domestic acetylene method fluid bed catalyzer for synthesizing vinyl acetate to use, coal system carrier active carbon.
3, said by right 2, it is characterized in that catalyst proportion is an active carbon: zinc oxide: zinc chloride=100: 23: 4.3(weight).
4, by right 3 described preparation Zinc oxide catalytics, it is characterized in that the spray solution temperature at 50～65 ℃, baking temperature is 80～100 ℃, and sintering temperature is 250～300 ℃, and the hot blast linear velocity is 0.2～0.3 meter per second.
5, be 1.5 by the right 4 described overall solution volume that it is characterized in that to almond or active carbon weight ratio, be made into mixed aqueous solution, in water-bath, be heated to 45 ℃, dried 2 hours down at 80 ℃ then, be warming up to 103 ± 2 ℃ of dryings again 2 hours, logical again nitrogen was warming up to 250 ℃ of constant temperature calcinings 5 hours after 15 minutes, made zinc nitrate be decomposed into zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86107833 CN86107833A (en) | 1986-11-17 | 1986-11-17 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86107833 CN86107833A (en) | 1986-11-17 | 1986-11-17 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86107833A true CN86107833A (en) | 1988-07-20 |
Family
ID=4803694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86107833 Pending CN86107833A (en) | 1986-11-17 | 1986-11-17 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
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| Country | Link |
|---|---|
| CN (1) | CN86107833A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328171C (en) * | 2004-04-26 | 2007-07-25 | 黄逸强 | Process for preparing basic zinc chloride of trace mineral supplement |
| CN100421798C (en) * | 2006-07-31 | 2008-10-01 | 中国石油化工集团公司 | Catalyst used for synthesis of vinyl acetate and its prepn. method |
| CN102371149A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | Method for preparing catalyst product for producing vinyl acetate |
| CN103934024A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of vinyl acetate and synthetic method of vinyl acetate |
| CN103934025A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of vinyl acetate by acetylene method and synthetic method of vinyl acetate |
| WO2015067133A1 (en) * | 2013-11-07 | 2015-05-14 | 中国石油化工股份有限公司 | Supported catalyst, preparation method therefor and use thereof, and method for preparation of isobutylene from halomethane |
| CN106268962A (en) * | 2016-07-14 | 2017-01-04 | 安徽海德石油化工有限公司 | One utilizes Synthesizing Vinyl Acetate from Acetylene loaded catalyst |
| CN109364970A (en) * | 2018-07-02 | 2019-02-22 | 石河子大学 | A kind of catalyst and preparation method and vinyl acetate synthesis method for vinyl acetate synthesis |
| CN109382084A (en) * | 2017-08-04 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of meso-porous carbon material and its preparation method and application |
| CN113649082A (en) * | 2021-08-13 | 2021-11-16 | 成都中科普瑞净化设备有限公司 | Method for preparing vinyl acetate catalyst by acetylene method |
-
1986
- 1986-11-17 CN CN 86107833 patent/CN86107833A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328171C (en) * | 2004-04-26 | 2007-07-25 | 黄逸强 | Process for preparing basic zinc chloride of trace mineral supplement |
| CN100421798C (en) * | 2006-07-31 | 2008-10-01 | 中国石油化工集团公司 | Catalyst used for synthesis of vinyl acetate and its prepn. method |
| CN102371149A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | Method for preparing catalyst product for producing vinyl acetate |
| CN103934024B (en) * | 2013-01-23 | 2016-05-18 | 中国石油化工股份有限公司 | The synthetic method of vinyl acetate catalyst and vinyl acetate |
| CN103934025A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of vinyl acetate by acetylene method and synthetic method of vinyl acetate |
| CN103934024A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of vinyl acetate and synthetic method of vinyl acetate |
| CN103934025B (en) * | 2013-01-23 | 2016-05-18 | 中国石油化工股份有限公司 | Acetylene method vinyl acetate catalyst and vinyl acetate synthetic method |
| WO2015067133A1 (en) * | 2013-11-07 | 2015-05-14 | 中国石油化工股份有限公司 | Supported catalyst, preparation method therefor and use thereof, and method for preparation of isobutylene from halomethane |
| US10087122B2 (en) | 2013-11-07 | 2018-10-02 | China Petroleum & Chemical Corporation | Supported catalyst, preparation method therefor and use thereof, and method for preparation of isobutylene from halomethane |
| CN106268962A (en) * | 2016-07-14 | 2017-01-04 | 安徽海德石油化工有限公司 | One utilizes Synthesizing Vinyl Acetate from Acetylene loaded catalyst |
| CN109382084A (en) * | 2017-08-04 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of meso-porous carbon material and its preparation method and application |
| CN109382084B (en) * | 2017-08-04 | 2021-08-06 | 中国石油化工股份有限公司 | Mesoporous carbon material and preparation method and application thereof |
| CN109364970A (en) * | 2018-07-02 | 2019-02-22 | 石河子大学 | A kind of catalyst and preparation method and vinyl acetate synthesis method for vinyl acetate synthesis |
| CN113649082A (en) * | 2021-08-13 | 2021-11-16 | 成都中科普瑞净化设备有限公司 | Method for preparing vinyl acetate catalyst by acetylene method |
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