CN100421798C - Catalyst used for synthesis of vinyl acetate and its prepn. method - Google Patents
Catalyst used for synthesis of vinyl acetate and its prepn. method Download PDFInfo
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- CN100421798C CN100421798C CNB2006100950014A CN200610095001A CN100421798C CN 100421798 C CN100421798 C CN 100421798C CN B2006100950014 A CNB2006100950014 A CN B2006100950014A CN 200610095001 A CN200610095001 A CN 200610095001A CN 100421798 C CN100421798 C CN 100421798C
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Abstract
A catalyst for synthesizing vinyl acetate from acetylene and acetic acid is prepared from activated carbon, zinc acetate and alkaline bismuth carbonate in mass ratio of 100: (27-40): 0.026 by excessive solution dipping method.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of the synthetic usefulness of a kind of vinyl acetate, particularly a kind of is primary raw material with acetylene and acetic acid, the Catalysts and its preparation method that the Fixed Bed Gas Phase synthesizing vinyl acetate is used.
Background technology
Acetylene gas is combined to the industrial catalyst of vinyl acetate, uses certain carrier to carry attached zinc acetate as catalyst always, uses charcoal to carry attached zinc acetate since nineteen twenty-two mugdan.Through a lot of researchs, finally replaced charcoal to make carrier, and almost be used as unique catalyst carrier afterwards at industrial active carbon with active carbon.As in " synthesizing vinyl acetate catalyst carrier, first volume of technical data " the 55th～71 page (1976), introduced Korea and adopted sawdust charcoal to carry attached zinc acetate catalyst; Japan has adopted the coconut husk charcoal to carry attached zinc acetate catalyst; At present, the domestic attached zinc acetate catalyst of various shell class carried by active carbon that still adopts based on coconut husk.In [Beijing Organic Chemical Plant " technological innovation compiles " 122 (1971)], also once narrated with silica gel and carried attached zinc oxide, aluminium oxide and zinc chloride catalyst, but these catalyst reactant liquor occurs in big pilot production of poor quality, catalyst has coking phenomenon, deadly defects such as silica-gel carrier insufficient strength.Gu Zhaofu " Japanese The Chemicals " V81.NO
2.298 point out in (1960): chemisorption, do not take place to acetylene, to synthesizing vinyl acetate yet catalytically inactive in independent zinc acetate or independent active carbon; Active carbon not only Dichlorodiphenyl Acetate zinc provides surface area but also has activation energy with the zinc acetate chemical bond.Certainly except that zinc acetate, the acetate of cadmium, mercury and bismuth carries and is attached on the active carbon, and the reaction of acetylene and acetic acid synthesizing vinyl acetate is all had catalytic action, but because the toxicity of zinc is less and cheap and easy to get, is used widely in industry.
At present synthesizing vinyl acetate mainly adopts fluid bed gas phase synthesizing vinyl acetate, mainly is the catalyst that fluid bed uses to the research of catalyzer for synthesizing vinyl acetate.Adopting the production technology of gas phase fixed bed synthesizing vinyl acetate for China then is that the seventies Sichuan vinylon plant in last century (hereinafter to be referred as river Wei Chang) has been introduced 90,000 tons/year natural gas acetylene method fixed bed synthesizing vinyl acetate device from France, what use at first is the catalyst that the Frenchman provides, this catalyst is carrier with the active carbon, zinc acetate is an active component, basic bismuth carbonate is a co-catalyst, wherein the content of zinc acetate is not higher than 26%, catalyst life is 110 days, and space time yield is 2.02t/m
3D; As seen there is active low, defective that the life-span is short in this catalyst, uses this catalyst, and it is changed, and number of times is frequent, the workman operates that labour intensity is big, transit time long, be prone to problem such as security incident.
Summary of the invention
The object of the present invention is to provide the catalyst that vinyl acetate synthesizes that is used for of a kind of active height, long service life.
Another object of the present invention is to provide above-mentioned Preparation of catalysts method.
The object of the present invention is achieved like this: a kind of synthetic catalyst of vinyl acetate that is used for, it is carrier with the active carbon, zinc acetate is an active component, basic bismuth carbonate is a co-catalyst, it is characterized in that: described active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 27～40: 0.026.
Active carbon in the catalyst: zinc acetate: the best proportioning of basic bismuth carbonate is 100: 30～40: 0.026.
Active carbon in the catalyst not only as the carrier of active component zinc acetate, strengthens the effect of catalyst efficiency in addition, thereby the quality quality of carrier active carbon is to all there being bigger influence in activity of such catalysts, selectivity and service life.In research process, the intensity, specific area, pore volume, pore size distribution that the inventor finds carrier active carbon is to there being bigger influence in service life of catalyst.Such as intensity and specific area that suitable bulk density helps regulating catalyst, iodine sorption value, specific area are big more, ash content is low more, show the adsorption capacity of active component zinc acetate strong more, activity is good more, intensity is big more, and catalyst is difficult for broken, helps prolonging the service life of catalyst; The suitable total pore volume of absorption, pore size distribution, pore radius helps giving full play to the effect of active carbon inner ratio surface area.So the bulk density of the active carbon that the present invention is selected is 300～500kg/m
3, iodine sorption value 〉=1000mg/g, intensity 〉=90%, ash≤12%, specific area 〉=1000m
2/ g adsorbs total pore volume 〉=0.6 * 10
-6m
3/ g, and pore size distribution (3～5nm) 〉=15%, average pore radius 〉=1nm.
The bulk density of above-mentioned active carbon is with 350～400kg/m
3For good.
Another object of the present invention is achieved in that a kind of synthetic Preparation of catalysts method of vinyl acetate that is used for, it is characterized in that: adopt the excess solution infusion process, with zinc oxide and acetic acid is primary raw material, add a small amount of waltherite in proportion, be made into 10～40% zinc acetate solutions at make-up tank, be heated to 60 ℃～120 ℃ circulations, absorb with the contact of the active carbon in the dipping tank and reach balance until absorption, stop the circulation of maceration extract, with catalyst drip-dry, drying, the storage for preparing.
The concrete preparation method of above-mentioned catalyst is characterized in that:
(1) preparation of zinc acetate solution: add a certain amount of single stage desalting water, acetic acid, zinc oxide and basic bismuth carbonate in make-up tank, be heated to 60 ℃～120 ℃, circulation is stirred, and is made into 10～40% zinc acetate solutions, and its pH value is 4～6.
(2) adding of active carbon: active carbon is sucked into the dipping tank from bucket with vavuum pump;
(3) dipping of active carbon: with pump the zinc acetate solution of (1) step gained is delivered to dipping tank as maceration extract, carry out the active carbon degassing earlier, and then flood, till zinc acetate solution concentration is constant;
(4) the drawing off and storing of catalyst: after dipping finishes, the zinc acetate maceration extract is returned make-up tank, with the catalyst drip-dry in the dipping tank, carry out dry storage then, the gained catalyst can use behind the reactor of packing into.
The concrete preparing process condition of above-mentioned zinc acetate maceration extract is: zinc acetate concentration is 10～40%, and dipping temperature is 80～100 ℃.
The preparing process of above-mentioned zinc acetate maceration extract: zinc acetate concentration is 18～35%, and dipping temperature is 80～100 ℃.
The drying of above-mentioned catalyst can adopt traditional seasoning to carry out drying.
This catalyst is after preparation is finished, owing to zinc acetate easily distils, after charcoal absorption zinc acetate content increases, standing time was above 3 days, just have zinc acetate and separate out, cause active component, reduced activity of such catalysts at activated carbon surface and inner skewness at activated carbon surface; And preparation of catalysts often needs one-month period, place general above 3 months, for the distribution problem of active component in the preservation problem that solves catalyst and the active carbon, the inventor advises adopting microwave drying, so that zinc acetate is reallocated in active carbon, solidified.
Adopt the concrete grammar of microwave drying as follows:, to send into microwave dryer by conveyer with the catalyst that preparation is finished; Regulating microwave power makes baking temperature progressively rise to 100 ℃ from 40 ℃; In dry run, in microwave machine, feed nitrogen, moisture is taken out of; In whole process, adopt the vacuum machine to control it for negative pressure, nitrogen is not leaked, to guarantee the content of nitrogen in the microwave machine; Utilize cooling system that nitrogen is cooled off, reclaim condensate liquid, nitrogen circulation is used.
The catalyst that adopts the method for the invention to make, its active component can distribute and solidify in carrier active carbon again, thereby reaches the performance that improves catalyst.Life of catalyst of the present invention breaks through 250 days, space-time yield 2.67t/m
3D, catalyst activity has improved 32.2%, and production cost descends significantly.It has overcome that original catalyst activity is low, the life-span is short, change that number of times is frequent, operation labour intensity is big, transit time long, easily go out a series of problems such as security incident; In a word, the present invention has not only reduced the more workload and the risk of catalyst changeout, but also has increased the effective production time, has reduced public work consumption, has good economic benefit.
In order to prove its effect, the inventor has made contrast test with catalyst of the present invention and Zinc oxide catalytic agent for synthesizing of acetic acid ethylene.
(1) catalytic activity
The catalytic activity contrast of catalyst that the method for the invention makes and the former French catalyst of river dimension station-service the results are shown in Table 1:
The present invention and other catalyst activity comparing result
| Catalyst type | The former French catalyst of river dimension station-service | Product of the present invention |
| Loaded catalyst (m 3) | 45 | 45 |
| Reaction temperature (℃) | 160～210 | 160～210 |
| Mole ratio (acetylene/acetic acid) | 5.0～12.0 | 5.0～12.0 |
| Air speed (h -1) | 250～350 | 250～350 |
| Space time yield (t/m 3d) | 2.02 | 2.67 |
As seen, in equal loadings, under the same reaction temperature condition, catalyst of the present invention is compared with the river former French zinc acetate catalyst of dimension station-service, and space time yield can improve about 32%.
(2) catalyst life
The former French catalyst life contrast of catalyst that the method for the invention makes and river dimension station-service the results are shown in Table 2:
The present invention and other life of catalyst comparing result
| Catalyst type | The former French catalyst of river dimension station-service | The present invention |
| Loaded catalyst | 45m 3 | 45m 3 |
| Reaction temperature (℃) | 200 | 200 |
| Mole ratio (acetylene/acetic acid) | 5.0～12.0 | 5.0～12.0 |
| Reaction time (h) | 100 | 100 |
| Air speed (h -1) | 240 | 350 |
| Active rate of descent (%) | 21.09 | 14.08 |
As seen, catalyst activity reduction amplitude of the present invention is little, shows that the life-span is long.
(3) synthesis reaction solution quality
Synthesizing vinyl acetate reactant liquor quality quality is an important symbol of weighing a kind of catalyst selectivity quality.The reactant liquor quality that catalyst of the present invention and the river former French catalyst of dimension station-service are produced in the synthesizing vinyl acetate process compares, and the results are shown in Table 3:
The reactant liquor comparing result of the present invention and other catalyst
| Catalyst type | The former French catalyst of river dimension station-service | The present invention |
| Reaction temperature (℃) | 190～210 | 190～210 |
| Acetaldehyde (%) | 1.24 | 1.25 |
| Crotonaldehyde content (%) | 0.05 | 0.02 |
| Specific activity (Δ t) | 0’46” | 0’45” |
As seen, the reaction temperature of the present invention and Zinc oxide catalytic is basic identical, but the quality of its reactant liquor is better relatively, and particularly this aldehyde of butylene is low.Show that selectivity of the present invention is better than the former French catalyst of river dimension station-service.
In a word, the present invention can effectively reduce the synthetic more stop frequency of catalyst changeout, reduce the post-processing difficulty of vinyl acetate rectification working process, improve the inherent quality of product and the economic benefit that vinyl acetate is produced, a series of disadvantages that the import activated-carbon catalyst exists have been overcome, realize the smooth transition of fixed bed vinyl acetate synthetic catalyst, improved the security of preparation catalyst, greatly reduced production difficulty and worker's labour intensity.
The specific embodiment
Embodiment 1: a kind of synthetic catalyst of vinyl acetate that is used for, it is characterized in that: it is carrier with the active carbon, zinc acetate is an active component, and basic bismuth carbonate is co-catalyst, wherein active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 27～32: 0.026.
Above-mentioned its concrete quality index of active carbon as carrier: bulk density is 410kg/m
3, iodine sorption value is 1090mg/g, and intensity is 95%, and ash is 11%, and specific area is 1080m
2/ g, adsorbing total pore volume is 0.68 * 10
-6m
3/ g, (3～5nm) is 16%, and average pore radius is 2nm in pore size distribution.
The concrete preparation method of above-mentioned catalyst is characterized in that:
(1) preparation of zinc acetate solution: add a certain amount of single stage desalting water, acetic acid, zinc oxide and basic bismuth carbonate in make-up tank, be heated to 80 ℃, circulation is stirred, and is made into 18.0 ± 1% zinc acetate solutions;
(2) adding of active carbon: active carbon is sucked into the dipping tank from bucket with vavuum pump;
(3) dipping of active carbon: with pump the zinc acetate solution of (1) step gained is delivered to dipping tank as maceration extract, carry out the active carbon degassing earlier, and then flooded 3.5 hours, till zinc acetate solution concentration is constant; The active component adsorbance is 27.87%.
(4) the drawing off and storing of catalyst: after dipping finishes, solution is returned make-up tank, with the catalyst drip-dry in the dipping tank, carry out dry storage according to conventional method then, the gained catalyst can use behind the reactor of packing into.
Use the catalyst that adopts the method for the invention to make, its main control parameters is that reaction temperature is 160 ℃～205 ℃, reaction pressure 0.03～0.05Mpa, and reactor pressure reduction is less than 0.03Mpa.Other just the same with original catalyst using method do not increase the difficulty and the workload of technology controlling and process and operation, and its operation result: this catalyst operation 224 days, space time yield is 2.35%t/m
3H, catalyst activity has improved 16.3% than original catalyst.
Embodiment 2: a kind of synthetic catalyst of vinyl acetate that is used for, it is characterized in that: it is carrier with the active carbon, zinc acetate is an active component, and basic bismuth carbonate is co-catalyst, wherein active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 33～35: 0.026.
Above-mentioned its concrete quality index of active carbon as carrier: bulk density is 400kg/m
3, iodine sorption value is 1143mg/g, and intensity is 97%, and ash is 7%, and specific area is 1180m
2/ g, adsorbing total pore volume is 0.7 * 10
-6m
3/ g, (3～5nm) is 16%, and average pore radius is more than the 2nm in pore size distribution.
The processing step of preparation catalyst is identical with embodiment 1, and different is: maceration extract zinc acetate concentration is 24%, and dipping temperature is 85 ℃～95 ℃, dip time 3.5 hours, and the adsorbance of active component is 33.03%.
Its operation result is that this catalyst has moved 308 days altogether, and space time yield is 2.67t/m
3H, catalyst activity has improved 32.2% than import catalyst.Production cost reduces significantly.
Embodiment 3: a kind of synthetic catalyst of vinyl acetate that is used for, it is characterized in that: it is carrier with the active carbon, zinc acetate is an active component, and basic bismuth carbonate is co-catalyst, wherein active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 36～40: 0.026.
Above-mentioned its concrete quality index of active carbon as carrier: bulk density is 400kg/m
3, iodine sorption value is 1143mg/g, and intensity is 97%, and ash is 7%, and specific area is 1180m
2/ g, adsorbing total pore volume is 0.7 * 10
-6m
3/ g, (3～5nm) is 16%, and average pore radius is more than the 2nm in pore size distribution.
The processing step of preparation catalyst is identical with embodiment 1, and different is: maceration extract zinc acetate concentration is 33%, and dipping temperature is 90 ℃～100 ℃, dip time 3.5 hours, and the adsorbance of active component is 39.8%.Because the zinc acetate content height of this catalyst, take conventional store method that the active component zinc acetate is separated out from activated carbon surface, reduce activity of such catalysts, adopt microwave drying, reinstall reactor production after the active component zinc acetate is solidified the catalyst drying.
Claims (10)
1. one kind is used for the synthetic catalyst of vinyl acetate, and it is carrier with the active carbon, and zinc acetate is an active component, and basic bismuth carbonate is a co-catalyst, it is characterized in that: described active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 27～40: 0.026.
2. the synthetic catalyst of vinyl acetate that is used for as claimed in claim 1, it is characterized in that: described active carbon: zinc acetate: the mass ratio of basic bismuth carbonate is 100: 30～40: 0.026.
3. the synthetic catalyst of vinyl acetate that is used for as claimed in claim 1 or 2, it is characterized in that: the bulk density of described active carbon is 300～500kg/m
3, iodine sorption value 〉=1000mg/g, intensity 〉=90%, ash≤12%, specific area 〉=1000m
2/ g adsorbs total pore volume 〉=0.6 * 10
-6m
3/ g, and pore size distribution (3～5nm) 〉=15%, average pore radius 〉=1nm.
4. the synthetic catalyst of vinyl acetate that is used for as claimed in claim 3, it is characterized in that: the bulk density of described active carbon is 350～400kg/m
3
5. as the described synthetic Preparation of catalysts method of vinyl acetate that is used for of the arbitrary claim of claim 1～4, it is characterized in that: adopt the excess solution infusion process, with zinc oxide and acetic acid is primary raw material, add a small amount of waltherite in proportion, be made into 10～40% zinc acetate solutions at make-up tank, be heated to 60 ℃～120 ℃ circulations, absorb with the contact of the active carbon in the dipping tank and reach balance until absorption, stop the circulation of maceration extract, with catalyst drip-dry, the drying for preparing.
6. the synthetic Preparation of catalysts method of vinyl acetate that is used for as claimed in claim 5, it is characterized in that: the preparation of (1) zinc acetate solution: in make-up tank, add a certain amount of single stage desalting water, acetic acid, zinc oxide and basic bismuth carbonate, be heated to 60 ℃～120 ℃, circulation is stirred, be made into 10～40% zinc acetate solutions, its pH value is 4～6;
(2) adding of active carbon: active carbon is sucked into the dipping tank from bucket with vavuum pump;
(3) dipping of active carbon: with pump the zinc acetate solution of (1) step gained is delivered to dipping tank as maceration extract, carry out the active carbon degassing earlier, and then flood, till zinc acetate solution concentration is constant;
(4) after dipping finishes, the zinc acetate maceration extract is returned make-up tank, with the catalyst drip-dry in the dipping tank, carry out drying then, the gained catalyst can use behind the reactor of packing into.
7. the synthetic Preparation of catalysts method of vinyl acetate that is used for as claimed in claim 6, it is characterized in that: zinc acetate concentration is 10～40%, dipping temperature is 80～100 ℃.
8. the synthetic Preparation of catalysts method of vinyl acetate that is used for as claimed in claim 7, it is characterized in that: zinc acetate concentration is 18～35%.
9. the synthetic Preparation of catalysts method of vinyl acetate that is used for as claimed in claim 5 is characterized in that: the dry or employing traditional drying method or the employing microwave of described catalyst carry out drying.
10. the synthetic Preparation of catalysts method of vinyl acetate that is used for as claimed in claim 9, it is characterized in that: adopting microwave drying is the catalyst that preparation is finished, and sends into microwave dryer by conveyer; Regulating microwave power makes baking temperature progressively rise to 100 ℃ from 40 ℃; In dry run, in microwave machine, feed nitrogen, moisture is taken out of; In whole process, adopt the vacuum machine to control it for negative pressure, nitrogen is not leaked, to guarantee the content of nitrogen in the microwave machine; Utilize cooling system that nitrogen is cooled off, reclaim condensate liquid, nitrogen circulation is used.
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| CN102029193A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Active carbon serving as catalyst carrier and treatment method and application thereof |
| CN102039180B (en) * | 2009-10-13 | 2012-08-22 | 黄石市高纯化工技术有限公司 | Catalyst for producing vinyl acetate and preparation method thereof |
| CN102284304A (en) * | 2009-12-31 | 2011-12-21 | 中国科学院成都有机化学有限公司 | Method for preparing high-efficiency catalyst for vinyl acetate synthesis by acetylene method |
| CN102218340B (en) * | 2010-04-16 | 2013-01-23 | 天华化工机械及自动化研究设计院有限公司 | Preparation method for synthesizing vinyl acetate catalyst by using acetylene gas phase method |
| CN102371149B (en) * | 2010-08-24 | 2015-08-05 | 中国石油化工集团公司 | A kind of preparation method of the catalyst product for the production of vinyl acetate |
| CN103030537B (en) * | 2011-10-10 | 2015-06-24 | 中国石油化工集团公司 | Method for rectifying acetaldehyde for acetylene-process vinyl acetate production technology |
| CN103111325B (en) * | 2011-11-16 | 2015-03-11 | 上海浦景化工技术股份有限公司 | Process for synthesizing vinyl acetate catalyst through acetylene method |
| CN103447083A (en) * | 2012-05-31 | 2013-12-18 | 冯良荣 | Catalyst for acetylene-method synthesis of vinyl acetate and preparation method thereof |
| 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 |
| CN103934030B (en) * | 2013-01-23 | 2016-05-18 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of synthesizing vinyl acetate |
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| CN103962178B (en) * | 2013-02-05 | 2016-05-18 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103962179B (en) * | 2013-02-05 | 2016-08-03 | 中国石油化工股份有限公司 | Catalyst for acetylene method vinyl acetate synthesis |
| CN104549496B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
| CN106268764B (en) * | 2015-05-11 | 2019-01-25 | 中国石油化工股份有限公司 | Prepare catalyst used in acetylene method vinyl acetate |
| CN106268944B (en) * | 2015-05-11 | 2019-05-14 | 中国石油化工股份有限公司 | For producing the catalyst of acetylene method vinyl acetate |
| CN105668610A (en) * | 2016-03-07 | 2016-06-15 | 昆明理工大学 | Method for preparing high-purity zinc oxide by using zinc-acetate-carrying waste activated carbon |
| CN107774322B (en) * | 2016-08-29 | 2019-11-08 | 中国石油化工股份有限公司 | It is used to prepare catalyst used in acetylene method vinyl acetate |
| CN107774321B (en) * | 2016-08-29 | 2019-11-08 | 中国石油化工股份有限公司 | Produce the catalyst of vinyl acetate |
| CN107790181B (en) * | 2016-08-29 | 2019-11-08 | 中国石油化工股份有限公司 | For synthesizing the catalyst of acetylene method vinyl acetate |
| CN108212172B (en) * | 2017-12-18 | 2020-11-27 | 西安凯立新材料股份有限公司 | Catalyst for hydrogenation of pyridine compounds and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU411892A1 (en) * | 1972-01-17 | 1974-01-25 | ||
| SU550700A1 (en) * | 1975-06-23 | 1977-03-15 | Организация П/Я М-5273 | A method of manufacturing a color kinescope screen |
| CN86107833A (en) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
-
2006
- 2006-07-31 CN CNB2006100950014A patent/CN100421798C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU411892A1 (en) * | 1972-01-17 | 1974-01-25 | ||
| SU550700A1 (en) * | 1975-06-23 | 1977-03-15 | Организация П/Я М-5273 | A method of manufacturing a color kinescope screen |
| CN86107833A (en) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
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