CN103084186B - For directly being prepared Catalysts and its preparation method and the purposes of ethanol by acetic acid - Google Patents
For directly being prepared Catalysts and its preparation method and the purposes of ethanol by acetic acid Download PDFInfo
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Abstract
The invention provides a kind of low cost acetic acid alcohol catalysis agent and its preparation method and application.More specifically, the invention provides a kind of catalyst for directly being prepared ethanol by acetic acid, described catalyst comprises the active ingredient compositions of load on carrier, described active ingredient compositions comprises platinum and tin, and the non-noble metal components of any one be selected from the group that is made up of copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc, the content of the platinum in wherein said catalyst is 0.01 ~ 0.09wt% and the weight ratio Pt/Sn of platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01 ~ 20wt%.This catalyst optionally can prepare ethanol at a lower temperature, and in catalyst, the load capacity of noble metal platinum is lower, and catalyst cost is lower, and catalyst performance and like product are on close level or better.
Description
Technical field
The invention belongs to field of catalytic chemistry, more specifically, the present invention relates to the catalyst for directly being prepared ethanol by acetic acid, and its production and use.
Background technology
Ethanol is as a kind of basic organic chemical industry raw material, of many uses at chemical industry and other industrial circle, can be used as disinfectant, solvent, also can be used as Organic Chemicals, for painting, the manufacturing of coating, dyestuff, ink and medicine etc., in addition also mainly as vehicle fuel.At present, China Chemical Industry is by ethanol market annual requirement at about 3,000,000 tons, and annual growth rate is 8%-10%.In alcohol fuel field, Chinese market current needs are about 1,500,000 tons/year, and estimate in the industry to welcome quick growth, the year two thousand twenty is expected to reach 1,000 ten thousand tons.
The production method of ethanol has ethylene hydration method and grain fermentation method, the industrial alcohol more than 70% of China is produced based on grain fermentation method, annual needs consumes a large amount of grain, in order to avoid striving grain with the people, the end of the year 2006, emergency notice is assigned by National Development and Reform Committee, and the raw material of China's alcohol fuel project should be adhered to based on non-grain.
Chinese newly-built acetic acid (namely in recent years, acetic acid) device goes into operation successively, domestic acetic acid production capacity sharply increases, and the Apparent con-sumption of acetic acid tends to be steady, cause production capacity seriously superfluous, acetic acid preparation of ethanol by hydrogenating technique, both can make full use of superfluous acetic acid resource, can provide new raw material sources again for the development of alcohol fuel.Economic aspect, acetic acid ethanol 1.5 tons of acetic acid can produce 1 ton of ethanol, and technical process is simple, and product purity is high, compare, have larger cost advantage with current grain fermentation legal system ethanol.
At present, even domestic not by the patent report of the direct ethanol processed of acetic acid, had disclosed patent report abroad, but great majority lack commercial operation.Such as, patent US2,607,807 report on ruthenium catalyst, and under the pressure of 700 ~ 950 bar, the yield of acetic acid ethanol can reach 88%, and the yield of ethanol is only 40% under the pressure of 200 bar.
Celanese Corp. of the U.S. is devoted to the research of the agent of acetic acid alcohol catalysis and technique in recent years always, discloses a series of patent.
Such as, patent US2011/0245546A1, with Pt-Co or Pd-Co for active component, with graphite, high-purity Si O
2with calcium silicates etc. for carrier prepares loaded catalyst, ethanol yield reaches as high as 68.2%, and catalyst now consists of Pt1wt%-Co10wt%/SiO
2.
Patent US2010/0029995A1 take Pt-Sn as active component, with graphite, high-purity Si O
2with calcium silicates etc. for carrier prepares loaded catalyst, ethanol yield reaches as high as 79.4%, and catalyst now consists of Pt1wt%-Sn1wt%/SiO
2.
Patent US2011/0098501A1, with Pt-Sn or Re-Pd for active component, with high-purity Si O
2for carrier prepares loaded catalyst, ethanol yield reaches as high as 54%, and catalyst now consists of Pt0.5wt%-Sn0.5wt%/SiO
2.
Patent US2011/0082322A1 take Pt1.6wt%-Sn1wt% as active component, when with high-purity Si O
2-TiO
2(10wt%) be carrier, ethanol yield reaches as high as 73.6%, when with high-purity Si O
2-Al
2o
3(7wt%) be carrier, ethanol yield reaches as high as 86.8%.
In addition, also have at SiO
2add the report of the carrier improvers such as calcium silicates, magnesium silicate, zinc oxide in carrier, the yield of its ethanol is all lower.
The acetic acid ethanol of Celanese Corp. is simple, and operating pressure is generally about 2.2MPa, and operating pressure is low, and commercial operation is large.But in the catalyst of Celanese Corp., the load capacity (that is, content) of noble metal platinum (Pt) is high, all at more than 0.1wt%, great majority are at 0.5 ~ more than 2wt%, and this makes the catalyst cost of preparation high.Meanwhile, though the non-noble metal catalyst of existing employing can reduce costs, its reaction temperature and reaction pressure require high, and condition is harsh, and commercial operation reduces greatly.
Summary of the invention
In order to overcome the problems referred to above of the existing catalyst directly preparing the reaction of ethanol for acetic acid, the object of this invention is to provide a kind of for acetic acid directly prepare ethanol low cost and can business-like catalyst.
On the one hand, the invention provides a kind of catalyst for directly being prepared ethanol by acetic acid, described catalyst comprises the active ingredient compositions of load on carrier, described active ingredient compositions comprises platinum and tin, and the non-noble metal components of any one be selected from the group that is made up of copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc, the content of the platinum in wherein said catalyst is 0.01 ~ 0.09wt% and the weight ratio Pt/Sn of platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01 ~ 20wt%.
In a preferred embodiment, described non-noble metal components is copper, molybdenum or nickel.
In a preferred embodiment, described carrier is selected from any one in the group be made up of silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide, is more preferably silica.
On the other hand, the invention provides a kind of method preparing above-mentioned catalyst, described method comprises: by the mixing of the salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components to obtain maceration extract; By on described impregnation fluid to described carrier to obtain catalyst precarsor; Obtain described catalyst with described catalyst precarsor being carried out drying roasting.
In a preferred embodiment, described maceration extract is impregnated on described carrier by equi-volume impregnating.
In a preferred embodiment, described maceration extract is the mixed liquor of the nitrate aqueous solution of the aqueous solution of chloroplatinic acid, the dilute nitric acid solution of tin oxalate and described non-noble metal components.
In a preferred embodiment, described catalyst precarsor dry 0.5 ~ 5 hour and roasting 1 ~ 8 hour at 400 ~ 600 DEG C at 100 ~ 130 DEG C.
In yet another aspect, the invention provides above-mentioned catalyst and directly prepared the purposes in ethanol by acetic acid, wherein acetic acid is by being ethanol with hydrogen reaction by selective hydrogenating reduction.
In a preferred embodiment, the described reaction directly preparing ethanol by acetic acid in the gas phase and carry out at the temperature of 200 ~ 300 DEG C.
In a further preferred embodiment, be 100: 1 ~ 1: 100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in described gas phase is 0.1 ~ 3MPa.
In a preferred embodiment, the described reaction directly being prepared ethanol by acetic acid is carried out at the temperature of 225 ~ 280 DEG C.
In a further preferred embodiment, be 1: 2 ~ 1: 100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in described gas phase is 1.0 ~ 2.5MPa.
Catalyst of the present invention is by using the composition of a certain proportion of Pt and Sn and other non-noble metal components as active component, Pt content in catalyst is reduced to 0.01 ~ 0.09wt%, not only reduce the cost of obtained catalyst, and catalyst of the present invention can prepare ethanol with high conversion and high yield by acetic acid selectivity, its catalytic efficiency is better than or is equivalent to existing high cost noble metal catalyst.
Detailed description of the invention
The object of the invention be to provide a kind of for acetic acid directly prepare ethanol low cost and can business-like catalyst.Object of the present invention is realized by such catalyst: described catalyst comprises the active ingredient compositions of load on carrier, the non-noble metal components of any one during described active ingredient compositions comprises platinum and tin and is selected from the group that is made up of copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc, the content of the platinum in wherein said catalyst is 0.01 ~ 0.09wt% and the weight ratio Pt/Sn of platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01 ~ 20wt%.
Utilize catalyst of the present invention, in a hydrogen atmosphere, direct for acetic acid selective hydrogenation can be generated ethanol.The reaction equation that acetic acid hydrogenation generates ethanol is as follows:
CH
3COOH+2H
2——→CH
3CH
20H+H
2O
Catalyst of the present invention can use the known various carriers for catalyst, and the example is including, but not limited to zeolite, iron oxide, silica, aluminium oxide, titanium oxide, zirconia, magnesia, calcium silicates, carbon, graphite and composition thereof.The carrier that the present invention preferably uses is silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide, more preferably uses silica as the carrier of catalyst of the present invention.
Preferably, the described non-noble metal components for catalyst of the present invention can be selected from the group that following metal is formed: copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc, more preferably, described non-noble metal components is copper, molybdenum or nickel.
In catalyst of the present invention, the content of tin usually with reference to the content of platinum, because weight ratio Pt/Sn is 1, if so in catalyst the content of platinum be 0.01 or 0.09wt%, then the content of tin is also 0.01 or 0.09wt%.
Catalyst of the present invention can be prepared by methods known in the art.Preferably, catalyst of the present invention is prepared by the following method, and described method comprises: by the mixing of the salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components to obtain maceration extract; By on described impregnation fluid to described carrier to obtain catalyst precarsor; Obtain described catalyst with described catalyst precarsor being carried out drying roasting.
In catalyst preparation process of the present invention, any method known in the art can be used to carry out metal impregnation.Preferably, described maceration extract is impregnated on described carrier by equi-volume impregnating, such as but not limited to, flooded as maceration extract by the mixed liquor of the nitrate aqueous solution using the aqueous solution of chloroplatinic acid, the dilute nitric acid solution of tin oxalate and described non-noble metal components, such as, flooded by equi-volume impregnating.
Preferably, in catalyst preparation process of the present invention, by described catalyst precarsor dry 0.5 ~ 5 hour and roasting 1 ~ 8 hour and obtain the catalyst expected at 400 ~ 600 DEG C at 100 ~ 130 DEG C.
Catalyst of the present invention can be applied to many application, especially may be used for acetic acid by being directly being prepared in the reaction of ethanol by acetic acid of ethanol with hydrogen reaction by selective hydrogenating reduction.The reaction directly being prepared ethanol by acetic acid can be carried out under gas phase or liquid-phase condition.Preferably, this reaction is carried out in gas phase (being gaseous state when namely all reactants arrive reactor).Operable reaction temperature preferably at about 200 ~ 300 DEG C, is more preferably 225 ~ 280 DEG C.Reaction pressure is not key influence factor to this reaction usually, and therefore this reaction pressure can lower than atmospheric pressure, atmospheric pressure or higher than atmospheric pressure.But, preferably, by the Stress control of this reaction in the pressure limit of 0.1 ~ 3MPa, preferably in the scope of about 1.0 ~ 2.5MPa.
Although in theory, in above-mentioned reaction, every mole of acetic acid consumes the hydrogen of 2 moles, but preferably, be about 100: 1 ~ 1: 100 as the acetic acid of reactant and the raw materials components mole ratio of hydrogen, be more preferably 1: 2 ~ 1: 100, the raw materials components mole ratio of such as acetic acid and hydrogen is 1: 5, to improve the conversion ratio of acetic acid.
For the reaction directly being prepared ethanol by acetic acid, conventional method can be adopted such as to adopt Agilent-6890 gas-chromatography to carry out qualitative and quantitative analysis to product.Before analysis, by calibrating gas and the normal fluid demarcation gas-chromatography of known composition.Wherein, prepass fid detector and PLOTQ capillary chromatographic column are used for following product possible in analytical reactions: methane, ethene, ethane, propylene, propane, methyl alcohol, ethanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and acetic acid.Rear passage TCD detector and 5A molecular sieve chromatography post are for analyzing possible following product: carbon dioxide etc.
The data gathered process by the following method:
Conversion ratio X: represent that the acetic acid occurring to transform accounts for the molar percentage of the acetic acid as raw material.The conversion ratio of acetic acid calculates as follows according to data from gas chromatography:
Selective S: represent that a certain product is based on the molar percentage transforming the acetic acid fallen.Selective is calculate as follows according to data from gas chromatography, for ethanol:
Yield Y: represent the mole percent of a certain product based on raw acetic acid.The yield of a certain product calculates as follows:
Following examples set forth the program for the preparation of the various catalyst used in the method for the invention.
Embodiment A
Preparation Pt0.01%-Sn0.01%/SiO
2catalyst (without non-noble metal components, for comparing)
The aqueous solution (0.67ml) of chloroplatinic acid (0.027g) and the dilute nitric acid solution (1ml) of tin oxalate (0.017g) are mixed and adds water and is made into the maceration extract of 72.6ml, join in 100g silica, limit edged stirs, the material obtained to be heated in the baking oven of 110 DEG C dry 2 hours gradually, then 500 DEG C of (heating rates in Muffle furnace, 2 DEG C/min) roasting 4 hours, both catalyst sample.
Embodiment B
Preparation Pt0.09%-Sn0.09%/SiO
2catalyst (without non-noble metal components, for comparing)
The aqueous solution (6.03ml) of chloroplatinic acid (0.243g) and the dilute nitric acid solution (1ml) of tin oxalate (0.153g) are mixed and adds water and is made into the maceration extract of 72.6ml, join in 100g silica, limit edged stirs, the material obtained to be heated in the baking oven of 120 DEG C dry 3 hours gradually, then 500 DEG C of (heating rates in Muffle furnace, 2 DEG C/min) roasting 4 hours, both catalyst sample.
Embodiment C
Preparation Pt0.09%-Sn0.09%-Ni15%/SiO
2catalyst (catalyst according to the invention)
The aqueous solution (50ml) of the aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and nickel nitrate (74.17g) is mixed and adds water and is made into the maceration extract of 72.6ml, join in 100g silica, limit edged stirs, the material obtained to be heated in the baking oven of 110 DEG C dry 2 hours gradually, then 600 DEG C of (heating rates in Muffle furnace, 2 DEG C/min) roasting 3 hours, both catalyst sample.
Embodiment D
Preparation Pt0.09%-Sn0.09%-Cu15%/SiO
2catalyst (catalyst according to the invention)
The aqueous solution (50ml) of the aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and copper nitrate (56.98g) is mixed and adds water and is made into the maceration extract of 72.6ml, join in 100g silica, limit edged stirs, the material obtained to be heated in the baking oven of 110 DEG C dry 2 hours gradually, then 400 DEG C of (heating rates in Muffle furnace, 2 DEG C/min) roasting 4 hours, both catalyst sample.
Embodiment E
Preparation Pt0.09%-Sn0.09%-Mo15%/SiO
2catalyst (catalyst according to the invention)
The aqueous solution (50ml) of the aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and ammonium molybdate (193.24g) is mixed and adds water and is made into the maceration extract of 72.6ml, join in 100g silica, limit edged stirs, the material obtained to be heated in the baking oven of 130 DEG C dry 2 hours gradually, then 500 DEG C of (heating rates in Muffle furnace, 2 DEG C/min) roasting 4 hours, both catalyst sample.
Catalyst sample is evaluated
Reactor used is stainless steel tubular reactor, the catalyst (being numbered Celanese 1 ~ 5 respectively) of the catalyst obtain embodiment A ~ E and aforementioned Celanese Corp. is placed in the middle part of reactor flat-temperature zone, does supporter up and down with stainless (steel) wire and quartz sand.Reaction raw materials is acetic acid and hydrogen, acetic acid is carried by measuring pump and is measured, hydrogen is exported by high-pressure cylinder and measures with mass flowmenter, the mol ratio of acetic acid and hydrogen is 1: 5, acetic acid and hydrogen reactor forward slip value and together with enter in reactor, react under 275 DEG C of pressure with 2.2MPa, extraction part reaction effluent is through gas chromatographic analysis composition and content.
Evaluating catalyst result is see table 1.
Table 1
Evaluating catalyst result as can be seen from table 1: (1) can prepare ethanol by catalysis acetic acid according to the catalyst of embodiment A ~ E (wherein the content of platinum be 0.01 ~ 0.09wt% and the weight ratio Pt/Sn of platinum and tin is 1); But containing being all be significantly less than catalyst according to the invention (catalyst of embodiment D ~ E, in its active component containing with good grounds non-noble metal components of the present invention) in acetic acid conversion or in ethanol yield according to the catalyst (embodiment A ~ B) of non-noble metal components of the present invention in active component; (2) catalyst according to the invention (catalyst of embodiment D ~ E) is being prepared in ethanol synthesis by acetic acid selectivity, and the conversion ratio of acetic acid is high (more than 96%), and the yield of ethanol is high (more than 82%); (3) catalyst according to the invention (catalyst of embodiment D ~ E) in ethanol yield with the noble metals content catalysts (Celanese 1 ~ 5) of existing Celanese Corp. be on close level or higher.
In addition, became originally from catalyst, in the catalyst of Celanese, the load capacity of platinum is more than 0.5wt%, calculates roughly by 1% platinum load capacity, and every gram of platinum calculates by 400 yuan (RMB), then the cost of catalyst per ton is at least 4,000,000 yuan.And in catalyst according to the invention, due to the content of precious metals pt low (being up to the 0.09wt% of whole catalyst), the base metal cost itself that load capacity is higher is simultaneously lower, too large impact can not be caused to catalyst cost, here with the load capacity of platinum for 0.09wt% calculates, then the cost of catalyst per ton is less than 400,000 yuan, lower than 1/10th of Celanese catalyst cost, therefore there is larger cost advantage, be economically more suitable for industrial applications.
Below to invention has been detailed description, but the present invention is not limited to detailed description of the invention described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and distortion can be made.Scope of the present invention is defined by the following claims.
Claims (13)
1. one kind for directly being prepared the catalyst of ethanol by acetic acid, described catalyst comprises the active ingredient compositions of load on carrier, described active ingredient compositions comprises platinum and tin, and the non-noble metal components of any one be selected from the group that is made up of copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc
The content of the platinum in wherein said catalyst is 0.01 ~ 0.09wt% and the weight ratio Pt/Sn of platinum and tin is 1, and the content of wherein said non-noble metal components is 15 ~ 20wt%.
2. catalyst according to claim 1, is characterized in that, described non-noble metal components is copper, molybdenum or nickel.
3. catalyst according to claim 1, is characterized in that, described carrier is selected from any one in the group be made up of silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide.
4. catalyst according to claim 3, is characterized in that, described carrier is silica.
5. prepare a method for the catalyst according to any one of claim 1-4, described method comprises:
By the mixing of the salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components to obtain maceration extract;
By on described impregnation fluid to described carrier to obtain catalyst precarsor; With
Described catalyst precarsor carried out drying roasting and obtain described catalyst.
6. method according to claim 5, is characterized in that, described maceration extract is impregnated on described carrier by equi-volume impregnating.
7. method according to claim 5, is characterized in that, described maceration extract is the mixed liquor of the nitrate aqueous solution of the aqueous solution of chloroplatinic acid, the dilute nitric acid solution of tin oxalate and described non-noble metal components.
8. method according to claim 5, is characterized in that, described catalyst precarsor dry 0.5 ~ 5 hour and roasting 1 ~ 8 hour at 400 ~ 600 DEG C at 100 ~ 130 DEG C.
9. the purposes in ethanol directly prepared by the catalyst according to any one of claim 1-4 by acetic acid, wherein acetic acid is by being ethanol with hydrogen reaction by selective hydrogenating reduction.
10. purposes according to claim 9, is characterized in that, the described reaction directly preparing ethanol by acetic acid in the gas phase and carry out at the temperature of 200 ~ 300 DEG C.
11. purposes according to claim 10, is characterized in that, be 100:1 ~ 1:100, and the pressure in described gas phase are 0.1 ~ 3MPa as the acetic acid of reactant and the mol ratio of hydrogen.
12. purposes according to claim 9, is characterized in that, the described reaction directly being prepared ethanol by acetic acid is carried out at the temperature of 225 ~ 280 DEG C.
13. purposes according to claim 12, is characterized in that, be 1:2 ~ 1:100, and the pressure in described gas phase are 1.0 ~ 2.5MPa as the acetic acid of reactant and the mol ratio of hydrogen.
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| CN104557453B (en) * | 2013-10-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of acetic acid preparation of ethanol through hydrogenation |
| CN104557454B (en) * | 2013-10-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of acetic acid Hydrogenation for high-quality ethanol |
| CN103691450B (en) * | 2014-01-06 | 2015-11-11 | 神华集团有限责任公司 | A kind of Catalysts and its preparation method of acetic acid hydrogenation ethanol |
| CN103691440B (en) * | 2014-01-06 | 2016-03-23 | 神华集团有限责任公司 | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| WO2015178459A1 (en) * | 2014-05-23 | 2015-11-26 | 三菱化学株式会社 | Metal-supported catalyst, metal-supported catalyst storage method, and alcohol manufacturing method |
| CN105566064B (en) * | 2014-10-14 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of method of acetic acid preparation of ethanol through hydrogenation |
| CN105709729B (en) * | 2014-12-03 | 2018-12-28 | 神华集团有限责任公司 | The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol |
| CN105709766A (en) * | 2014-12-03 | 2016-06-29 | 神华集团有限责任公司 | Catalyst for preparing ethanol through acetic acid hydrogenation, preparation method of catalyst and method for preparing ethanol through acetic acid hydrogenation |
| CN108707058A (en) * | 2018-04-11 | 2018-10-26 | 华东师范大学 | A kind of two-step method inverting biological grease is the method for linear alpha-alkene |
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| CN102658165B (en) * | 2012-04-06 | 2014-11-05 | 华东理工大学 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
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| CN102304018A (en) * | 2008-07-31 | 2012-01-04 | 国际人造丝公司 | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
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