CN103170352A - Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof - Google Patents
Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN103170352A CN103170352A CN2013101035361A CN201310103536A CN103170352A CN 103170352 A CN103170352 A CN 103170352A CN 2013101035361 A CN2013101035361 A CN 2013101035361A CN 201310103536 A CN201310103536 A CN 201310103536A CN 103170352 A CN103170352 A CN 103170352A
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Abstract
The invention provides a sec-butyl acetate hydrogenation catalyst and a preparation method and application thereof. The catalyst contains active component elements of copper and palladium and assistant component elements of zinc and zirconium used for sec-butyl acetate hydrogenation,, wherein the catalyst also contains an alkaline earth element. Application of the sec-butyl acetate hydrogenation catalyst is also provided by the invention. The catalyst disclosed by the invention has the advantages of good low-temperature reaction activity, high product selectivity and the like when applied to the sec-butyl acetate hydrogenation reaction process.
Description
Technical field
The present invention relates to comprise the technical field of the catalyst of metal or oxide, be specifically related to a kind of Catalysts and its preparation method and application of sec-butyl acetate hydrogenation.
Background technology
Propagation and employment along with sec-butyl acetate on market and production-scale continuous expansion, sec-butyl acetate becomes a kind of large chemical products gradually, and the market price is also relatively cheap, and the exploitation of its downstream product has caused extensive concern.
As one of sec-butyl acetate downstream product, the sec-butyl alcohol purposes is wider.Sec-butyl alcohol is the raw material of synthetic MEK, because the apparent consumption of MEK is huge, has caused the market demand of its raw materials for production sec-butyl alcohol also very large.Sec-butyl alcohol also can be used as anti emulsifier, dye dispersant, dehydrating agent, paint stripper, industrial detergent etc. in addition; Also can be used as the manufacturing of plasticizer, oil extraction agent, wetting agent, spices etc.At present, the route of the synthetic sec-butyl alcohol of industry is mainly to adopt the butylene hydration method, but because this method ubiquity reaction conversion ratio is low, therefore the shortcoming that energy consumption is high, need to further seek the new method of the synthetic sec-butyl alcohol of energy-saving and environmental protection.
Ethanol is as another important downstream product of sec-butyl acetate, and it has purposes quite widely, except as fuel, make outside beverage and essence, and be also a kind of important Organic Chemicals.The industrial making method of ethanol mainly contains fermentation method and ethylene hydration method.Fermentation method is a kind of important method of ethanol production, if further develop the problem that the grain fermentation can produce grain security.And the ethene that ethylene hydration method produces take petroleum cracking is as raw material, and due to the few oily many coals of China, its development also is limited by very large.Therefore, development can be given full play to the advantage of rich coal resources in China with the variation route of the leading synthesizing alcohol of acetic acid, can possess and the advantage of traditional grain fermentation with the petroleum path competition.Simultaneously, can alleviate on the one hand the predicament that present domestic acetic acid industry is in the serious surplus of production capacity, market continued downturn; On the other hand, due to the unstability of the non-renewable and oildom of oil, alcohol fuel can be extenuated the problems such as energy security that produce therefrom to a certain extent.
Therefore, exploitation sec-butyl acetate downstream product tool is of great significance, and can extend the sec-butyl acetate industrial chain, solves the problem of acetic acid industry production capacity surplus.At present, be specifically designed to catalyst and the hydrogenation technique that the sec-butyl acetate catalytic hydrogenation prepares sec-butyl alcohol and ethanol and have no relevant report.
Summary of the invention
The object of the present invention is to provide Catalysts and its preparation method and the application of the sec-butyl acetate catalytic hydrogenation that a kind of low temperature active is good, product selectivity is high.
For realizing the aforementioned techniques purpose, on the one hand, the invention provides a kind of catalyst of sec-butyl acetate catalytic hydrogenation, contain active component element and adjuvant component element as the sec-butyl acetate hydrogenation in this catalyst, described active component element is copper and palladium, described adjuvant component element is zinc and zirconium, wherein, also contains alkaline earth element in described catalyst.
Sec-butyl acetate hydrogenation catalyst of the present invention, the mass ratio that it is characterized in that copper, palladium element, zinc element, zr element and alkaline earth element is 100:1-10:60-220:5-70:10-50, more preferably 100:3-5:120-160:20-40:20-40.
On the other hand, the invention provides a kind of preparation method of catalyst of sec-butyl acetate hydrogenation, the method comprises:
Under deposition condition, at first, after being contacted in water with precipitating reagent, the soluble-salt of the soluble-salt of adjuvant component element and alkaline earth element obtains containing the suspension of solids of sedimentation; Secondly, contact the soluble-salt of active component element afterwards in aforementioned suspension with precipitating reagent, filtration obtains solid sediment.In addition, also comprise subsequent wash, drying and the roasting of solid sediment.Wherein, described active component element is copper and palladium, and described adjuvant component element is zinc and zirconium.
The preparation method of catalyst according to the present invention, described optional wider range that contains as the kind of the compound of the component element of sec-butyl acetate hydrogenation catalyst.For the present invention, in above-mentioned preparation method, the soluble-salt of active component elemental copper used is copper sulphate, or copper nitrate, or copper chloride, or copper acetate, or copper formate; The soluble-salt of active component element palladium used is palladium bichloride, or palladium nitrate; The soluble-salt of adjuvant used component element zinc is zinc sulfate, or zinc nitrate, or zinc chloride, or zinc acetate; The soluble-salt of adjuvant used component element zirconium is zirconium sulfate, or zirconium nitrate, or zirconyl nitrate, or zirconium chloride, or zirconyl chloride; The soluble-salt of alkaline earth element used is alkali nitrates, or chlorate.
The preparation method of catalyst according to the present invention, optional wider range of described deposition condition, for the present invention, preferred described deposition condition comprises: temperature is 40-80 ℃, the pH value is 7-8 (generally referring to endpoint pH).In the present invention, the condition of precipitation refers to the condition kept in coprecipitation process, can keep by the charging rate of controlling precipitating reagent the pH value of precipitation process.
The preparation method of catalyst according to the present invention, optional wider range of the condition of described drying, the condition of roasting is for the present invention, in order further to improve the hydrogenation activity of the catalyst for preparing, the condition of described drying comprises: temperature is 80-120 ℃, and the time is 4-20h; The condition of roasting comprises: temperature is 350-550 ℃, and the time is 4-10h.
The preparation method of catalyst according to the present invention, the precipitating reagent that the routine of prior art is used all can be used for the present invention.For the present invention, preferred described precipitating reagent is inorganic base, and more preferably described precipitating reagent is alkali metal hydroxide.
In the present invention, if no special instructions, described precipitation process is all carried out under stirring condition.
On the one hand, the invention provides the application of a kind of catalyst of the present invention in the sec-butyl acetate hydrogenation reaction again.Concrete application process is as follows:
First catalyst is reduced under reducing atmosphere: reduction temperature is 160-240 ℃, and reduction pressure is normal pressure-5MPa, and the recovery time is 4-10h; Then, under the existence of the hydrogenation catalyst of the present invention that process is reduced, sec-butyl acetate is contacted with hydrogen.
According to the application process of hydrogenation catalyst of the present invention, sec-butyl acetate and hydrogen contact conditions are reaction temperature 180-260 ℃, reaction pressure 3-10MPa, hydrogen and sec-butyl acetate mol ratio 10-200, ester air speed 0.1-0.8h
-1
Described reducing atmosphere is the mist of pure hydrogen or hydrogen and inert gas.
The present invention makes catalyst of the present invention have higher low temperature active and selective for the reaction of sec-butyl acetate hydrogenation by introduce the second active component Pd element in the catalyst of sec-butyl acetate hydrogenation, this is due to active component Cu more easily is reduced, changed simultaneously catalyst surface Cu species and distribution situation thereof, the synergy of Pd and Cu has improved reactivity and selectivity of product.
The present invention is by introducing alkaline earth element in the catalyst of sec-butyl acetate hydrogenation, decentralization and the stability of copper crystallite have been improved on the one hand, increased to a certain extent on the other hand the alkalescence of catalyst, avoid dissociating or the generation of the accessory substances such as dehydration of hydrogenation products of raw material, thereby improved the selective of hydrogenation products.
The present invention is in the process of preparation sec-butyl acetate hydrogenation catalyst, adopt the method for fractional precipitation first adjuvant component element and alkaline earth element to be carried out co-precipitation, described solid sediment and the active component element that will obtain precipitate again, make the catalyst that obtains according to method of the present invention be used for the sec-butyl acetate hydrogenation reaction and have higher activity, this is because active component mainly is distributed in catalyst coating, weakened simultaneously the strong interaction of active component and adjuvant component, thereby provide due to more hydrogenation activity species.
Catalyst provided by the invention and application are applicable to the sec-butyl acetate hydrogenation reaction, also are applicable to the hydrogenation reaction that other contains the raw material of ester.
Catalyst of the present invention has advantages of that low-temperature reactivity is good and selectivity of product is high, and for example, under the condition of optimizing, when the sec-butyl acetate conversion ratio reached 100%, ethanol selectively can reach more than 99.5%, and sec-butyl alcohol selectively can reach 100%.
The specific embodiment
Further illustrate by the following examples effect of the present invention, but and do not mean that the restriction range of application of the present invention.
Embodiment 1
Kaolinite Preparation of Catalyst:
With 189.0 gram Zn (NO
3)
2, 20.8 gram ZrCl
4With 50.1 gram Mg (NO
3)
2Be made into metal mixed solution 1 with deionized water, with (NH
4)
2CO
3The aqueous solution and metal mixed solution 1 carry out co-precipitation under 80 ℃ of water-baths, continuous stirring condition, the control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; With 119.3 gram Cu (NO
3)
2With 4.4 gram Pd (NO
3)
2Be made into metal mixed solution 2 with deionized water, with (NH
4)
2CO
3The aqueous solution and metal mixed solution 2 80 ℃ of water-baths, constantly stir and solids 1 existence condition under carry out co-precipitation, controls endpoint pH is 7-8, finally whole metal ions is solids 2 by co-precipitation; At last solids 25 hour is namely got catalyst A in 450 ℃ of roastings 120 ℃ of oven dry after 10 hours, catalyst and composition thereof see Table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Getting the 10.0 gram catalyst A diameter of packing into is that 12mm, length are in the fixed bed stainless steel reactor of 120cm, reactor up and down two ends filling quartz sand, middle loading catalyst, to guarantee that catalyst in the flat-temperature zone of reactor (if no special instructions, following examples and Comparative Examples are all used this reactor, type of feed is also consistent), at first carry out catalyst reduction in this reactor, then carry out the sec-butyl acetate hydrogenation reaction;
Wherein, the catalyst reduction condition comprises: temperature is 180 ℃, and pressure is 1.0MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 10h;
The sec-butyl acetate hydroconversion condition comprises: temperature is 180-230 ℃, and pressure is 5MPa, and the hydrogen ester mol ratio is 100:1, and the ester liquid hourly space velocity (LHSV) is 0.5h
-1, reaction result sees Table 1.
Embodiment 2
Kaolinite Preparation of Catalyst:
With 80.5 gram ZnSO
4, 40.4 gram Zr (NO
3)
4With 30.1 gram CaCl
2Be made into metal mixed solution 1 with deionized water, the NaOH aqueous solution and metal mixed solution 1 are carried out co-precipitation under 60 ℃ of water-baths, continuous stirring condition, the control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; With 68.0 gram CuSO
4With 1.4 gram PdCl
2Be made into metal mixed solution 2 with deionized water, with the NaOH aqueous solution and metal mixed solution 2 60 ℃ of water-baths, constantly stir and solids 1 existence condition under carry out co-precipitation, the control endpoint pH is 7-8, and final whole metal ion is solids 2 by co-precipitation; At last solids 26 hour is namely got catalyst B in 480 ℃ of roastings 100 ℃ of oven dry after 15 hours, catalyst and composition thereof see Table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 gram catalyst B and pack in the fixed bed stainless steel reactor, at first carry out catalyst reduction in this reactor, then carry out the sec-butyl acetate hydrogenation reaction;
Wherein, the catalyst reduction condition comprises: temperature is 240 ℃, and pressure is normal pressure, and reducing atmosphere is the hydrogen of argon-dilution, and the recovery time is 4h;
The sec-butyl acetate hydroconversion condition comprises: temperature is 190-250 ℃, and pressure is 3MPa, and the hydrogen ester mol ratio is 60:1, and the ester liquid hourly space velocity (LHSV) is 0.6h
-1, reaction result sees Table 1.
Embodiment 3
Kaolinite Preparation of Catalyst:
With 136.0 gram ZnCl
2, 64.3 gram Zr (SO
4)
2With 5.3 gram SrCl
2Be made into metal mixed solution 1 with deionized water, the KOH aqueous solution and metal mixed solution 1 are carried out co-precipitation under 40 ℃ of water-baths, continuous stirring condition, the control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; With 62.3 gram CuCl
2With 4.9 gram PdCl
2Be made into metal mixed solution 2 with deionized water, with the KOH aqueous solution and metal mixed solution 2 60 ℃ of water-baths, constantly stir and solids 1 existence condition under carry out co-precipitation, the control endpoint pH is 7-8, and final whole metal ion is solids 2 by co-precipitation; At last solids 24 hour is namely got catalyst C in 550 ℃ of roastings 80 ℃ of oven dry after 20 hours, catalyst and composition thereof see Table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 gram catalyst C and pack in the fixed bed stainless steel reactor, at first carry out catalyst reduction in this reactor, then carry out the sec-butyl acetate hydrogenation reaction (weight ratio of sec-butyl alcohol and sec-butyl acetate is 1:1) of sec-butyl alcohol dilution;
Wherein, the catalyst reduction condition comprises: temperature is 160 ℃, and pressure is 5.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 10h;
The sec-butyl acetate hydroconversion condition comprises: temperature is 180-230 ℃, and pressure is 3MPa, and hydrogen and sec-butyl acetate mol ratio are 10:1, and the ester liquid hourly space velocity (LHSV) is 0.1h
-1, reaction result sees Table 1.
Embodiment 4
Kaolinite Preparation of Catalyst:
With 183.0 gram Zn (CH
3COO)
2, 13.8 gram ZrO (NO
3)
2With 82.2 gram BaCl
2Be made into metal mixed solution 1 with deionized water, with Li
2CO
3The aqueous solution and metal mixed solution 1 carry out co-precipitation under 60 ℃ of water-baths, continuous stirring condition, the control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; With 308.1 gram Cu (CH
3COO)
2With 2.4 gram Pd (NO
3)
2Be made into metal mixed solution 2 with deionized water, with Li
2CO
3The aqueous solution and metal mixed solution 2 80 ℃ of water-baths, constantly stir and solids 1 existence condition under carry out co-precipitation, controls endpoint pH is 7-8, finally whole metal ions is solids 2 by co-precipitation; At last solids 2 10 hour is namely got catalyst D in 350 ℃ of roastings 120 ℃ of oven dry after 4 hours, catalyst and composition thereof see Table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 gram catalyst D and pack in the fixed bed stainless steel reactor, at first carry out catalyst reduction in this reactor, then carry out the sec-butyl acetate hydrogenation reaction;
Wherein, the catalyst reduction condition comprises: temperature is 230 ℃, and pressure is 3.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 5h;
The sec-butyl acetate hydroconversion condition comprises: temperature is 230-260 ℃, and pressure is 10MPa, and the hydrogen ester mol ratio is 200:1, and the ester liquid hourly space velocity (LHSV) is 0.8h
-1, reaction result sees Table 1.
Embodiment 5
Kaolinite Preparation of Catalyst:
With 169.0 gram Zn (NO
3)
2, 38.0 gram Zr (NO
3)
4With 20.6 gram BeCl
2Be made into metal mixed solution 1 with deionized water, with NaHCO
3The aqueous solution and metal mixed solution 1 carry out co-precipitation under 60 ℃ of water-baths, continuous stirring condition, the control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; With 111.7 gram Cu (HCOO)
2With 0.5 gram Pd (NO
3)
2Be made into metal mixed solution 2 with deionized water, with NaHCO
3The aqueous solution and metal mixed solution 2 60 ℃ of water-baths, constantly stir and solids 1 existence condition under carry out co-precipitation, controls endpoint pH is 7-8, finally whole metal ions is solids 2 by co-precipitation; At last solids 26 hour is namely got catalyst E in 450 ℃ of roastings 120 ℃ of oven dry after 4 hours, catalyst and composition thereof see Table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 gram catalyst E and pack in the fixed bed stainless steel reactor, at first carry out catalyst reduction in this reactor, then carry out the sec-butyl acetate hydrogenation reaction;
Wherein, the catalyst reduction condition comprises: temperature is 190 ℃, and pressure is 2.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 6h;
The sec-butyl acetate hydroconversion condition comprises: temperature is 210-260 ℃, and pressure is 5MPa, and the hydrogen ester mol ratio is 80:1, and the ester liquid hourly space velocity (LHSV) is 0.8h
-1, reaction result sees Table 1.
Comparative Examples 1
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is not add Pd (NO in preparation process
3)
2, all the other conditions are all identical, obtain catalyst D1.Catalyst reduction and sec-butyl acetate hydrogenation conditions are all with embodiment 1, and reaction result sees Table 1.
Comparative Examples 2
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is not add Mg (NO in preparation process
3)
2, all the other conditions are all identical, obtain catalyst D2.Catalyst reduction and sec-butyl acetate hydrogenation conditions are all with embodiment 1, and reaction result sees Table 1.
Comparative Examples 3
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is, adjuvant component Zn (NO in preparation process
3)
2, ZrCl
4, Mg (NO
3)
2With active component Cu (NO
3)
2And Pd (NO
3)
2Simultaneously with (NH
4)
2CO
3Precipitating reagent carries out co-precipitation, and all the other conditions are all identical, obtains catalyst D3.Catalyst reduction and sec-butyl acetate hydrogenation conditions are all with embodiment 1, and reaction result sees Table 1.
Comparative Examples 4
The commercial Cu base of outsourcing ester through hydrogenation catalyst FHE, catalyst reduction and sec-butyl acetate hydrogenation conditions are all with embodiment 1, and reaction result sees Table 1.
Table 1
Claims (10)
1. sec-butyl acetate hydrogenation catalyst, it is characterized in that: this catalyst contains as the copper of sec-butyl acetate hydrogenation and palladium active component element and zinc and zirconium adjuvant component element, wherein, also contains alkaline earth element in described catalyst.
2. catalyst according to claim 1, it is characterized in that: the mass ratio of copper, palladium element, zinc element, zr element and alkaline earth element is 100:1-10:60-220:5-70:10-50.
3. catalyst according to claim 2, it is characterized in that: the mass ratio of copper, palladium element, zinc element, zr element and alkaline earth element is 100:3-5:120-160:20-40:20-40.
4. the preparation method of a sec-butyl acetate hydrogenation catalyst, it is characterized in that: the method comprises:
Under deposition condition, at first, after being contacted in water with precipitating reagent, the soluble-salt of the soluble-salt of adjuvant component element and alkaline earth element obtains containing the suspension of solids of sedimentation; Secondly, contact the soluble-salt of active component element afterwards in aforementioned suspension with precipitating reagent, filtration obtains solid sediment; Then, also comprise subsequent wash, drying and the roasting of solid sediment.
5. method for preparing catalyst according to claim 4, it is characterized in that: described precipitating reagent is inorganic base.
6. method for preparing catalyst according to claim 5, it is characterized in that: described precipitating reagent is alkali metal hydroxide.
7. the described preparation method of any one according to claim 4-6, it is characterized in that: the condition of described drying comprises: temperature is 80-120 ℃, the time is 4-20h; The condition of roasting comprises: temperature is 350-550 ℃, and the time is 4-10h.
8. the application of the catalyst of a sec-butyl acetate hydrogenation is characterized in that:
First the described catalyst of 1-3 is reduced under reducing atmosphere: reduction temperature is 160-240 ℃, and reduction pressure is normal pressure-5MPa, and the recovery time is 4-10h; Then, under the existence of the sec-butyl acetate hydrogenation catalyst that process is reduced, sec-butyl acetate is contacted with hydrogen.
9. application according to claim 8 is characterized in that: the condition that described sec-butyl acetate contacts with hydrogen is reaction temperature 180-260 ℃, reaction pressure 3-10MPa, hydrogen and sec-butyl acetate mol ratio 10-200, ester air speed 0.1-0.8h
-1
10. application according to claim 8 is characterized in that: described reducing atmosphere is the mist of pure hydrogen or hydrogen and inert gas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370722A (en) * | 2014-12-11 | 2015-02-25 | 湖南瑞源石化股份有限公司 | Butanone preparation and refining method |
| CN104549322A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Catalyst for producing 1,4-cyclohexanedimethanol by hydrogenation and preparation and application thereof |
| CN105032439A (en) * | 2015-07-29 | 2015-11-11 | 上海华谊（集团）公司 | Catalyst for producing sec-butyl alcohol and ethyl alcohol through sec-butyl acetate hydrogenationm, preparation method and application thereof |
| CN105126798A (en) * | 2015-07-29 | 2015-12-09 | 上海华谊（集团）公司 | Catalyst for combined production of sec-butyl alcohol and ethanol by sec-butyl acetate hydrogenation and its preparation method and use |
| CN105618062A (en) * | 2014-11-26 | 2016-06-01 | 江苏海普功能材料有限公司 | Sec-butyl acetate hydrogenation catalyst, preparation method and application thereof |
| CN107540522A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of production technology of sec-butyl alcohol |
| CN113713829A (en) * | 2021-10-09 | 2021-11-30 | 凯瑞环保科技股份有限公司 | Preparation method of sec-butyl acetate hydrogenation catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011053365A1 (en) * | 2009-10-26 | 2011-05-05 | Celanese International Corporation | Processes for making ethanol from acetic acid |
| CN102146019A (en) * | 2011-02-22 | 2011-08-10 | 湖南长岭石化科技开发有限公司 | Method for preparing alcohols from olefin |
| CN102814184A (en) * | 2012-09-12 | 2012-12-12 | 西北化工研究院 | Catalyst for preparing ethylene glycol by hydrogenating oxalate and preparation method thereof |
| CN102946994A (en) * | 2010-04-21 | 2013-02-27 | Sk新技术株式会社 | Nanometer-sized copper-based catalyst, production method thereof, and alcohol production method using the same through direct hydrogenation of carboxylic acid |
-
2013
- 2013-03-28 CN CN201310103536.1A patent/CN103170352B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011053365A1 (en) * | 2009-10-26 | 2011-05-05 | Celanese International Corporation | Processes for making ethanol from acetic acid |
| CN102946994A (en) * | 2010-04-21 | 2013-02-27 | Sk新技术株式会社 | Nanometer-sized copper-based catalyst, production method thereof, and alcohol production method using the same through direct hydrogenation of carboxylic acid |
| CN102146019A (en) * | 2011-02-22 | 2011-08-10 | 湖南长岭石化科技开发有限公司 | Method for preparing alcohols from olefin |
| CN102814184A (en) * | 2012-09-12 | 2012-12-12 | 西北化工研究院 | Catalyst for preparing ethylene glycol by hydrogenating oxalate and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549322A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Catalyst for producing 1,4-cyclohexanedimethanol by hydrogenation and preparation and application thereof |
| CN105618062A (en) * | 2014-11-26 | 2016-06-01 | 江苏海普功能材料有限公司 | Sec-butyl acetate hydrogenation catalyst, preparation method and application thereof |
| CN104370722A (en) * | 2014-12-11 | 2015-02-25 | 湖南瑞源石化股份有限公司 | Butanone preparation and refining method |
| CN104370722B (en) * | 2014-12-11 | 2015-08-26 | 湖南瑞源石化股份有限公司 | Preparation and the refining method of butanone |
| CN105032439A (en) * | 2015-07-29 | 2015-11-11 | 上海华谊（集团）公司 | Catalyst for producing sec-butyl alcohol and ethyl alcohol through sec-butyl acetate hydrogenationm, preparation method and application thereof |
| CN105126798A (en) * | 2015-07-29 | 2015-12-09 | 上海华谊（集团）公司 | Catalyst for combined production of sec-butyl alcohol and ethanol by sec-butyl acetate hydrogenation and its preparation method and use |
| CN105126798B (en) * | 2015-07-29 | 2018-04-13 | 上海华谊（集团）公司 | Sec-butyl acetate is hydrogenated with catalyst of coproduction sec-butyl alcohol and ethanol and its preparation method and application |
| CN107540522A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of production technology of sec-butyl alcohol |
| CN107540522B (en) * | 2016-06-29 | 2020-09-08 | 中国石油化工股份有限公司 | Production process of sec-butyl alcohol |
| CN113713829A (en) * | 2021-10-09 | 2021-11-30 | 凯瑞环保科技股份有限公司 | Preparation method of sec-butyl acetate hydrogenation catalyst |
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