CN103170352B - 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
- Publication number
- CN103170352B CN103170352B CN201310103536.1A CN201310103536A CN103170352B CN 103170352 B CN103170352 B CN 103170352B CN 201310103536 A CN201310103536 A CN 201310103536A CN 103170352 B CN103170352 B CN 103170352B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sec
- butyl acetate
- hydrogen
- acetate hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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 the technical field of the catalyst comprising metal or oxide, be specifically related to a kind of Catalysts and its preparation method and application of sec-butyl acetate hydrogenation.
Background technology
Along with sec-butyl acetate propagation and employment commercially 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 causes extensive concern.
As one of sec-butyl acetate downstream product, sec-butyl alcohol purposes is wider.Sec-butyl alcohol is the raw material of synthesis MEK, and because the apparent consumption of MEK is huge, the market demand that result in its raw materials for production sec-butyl alcohol is 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 manufacture of plasticizer, oil extraction agent, wetting agent, spices etc.At present, the route of commercial synthesis sec-butyl alcohol mainly adopts butylene hydration method, but due to this method ubiquity reaction conversion ratio low, the shortcoming that energy consumption is high, therefore, needs the new method of the synthesis sec-butyl alcohol seeking energy-saving and environmental protection further.
Ethanol is as another important downstream product of sec-butyl acetate, and it has purposes quite widely, and except being used as fuel, manufacturing outside beverage and essence, is 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, the problem that grain fermentation can produce grain security if further develop.And the ethene that ethylene hydration method produces with petroleum cracking is for raw material, due to the few oily many coals of China, its development is also limited by very large.Therefore, develop with the variation route of the leading synthesizing alcohol of acetic acid, the advantage of rich coal resources in China can be given full play to, the advantage of to ferment with traditional grain and competing with petroleum path can be possessed.Meanwhile, the predicament that current domestic acetic acid industry is in the serious surplus of production capacity, market continued downturn can be alleviated on the one hand; On the other hand, due to the non-renewable of oil and the unstability of oildom, alcohol fuel can extenuate the problems such as the energy security produced therefrom to a certain extent.
Therefore, exploitation sec-butyl acetate downstream product tool is of great significance, and can extend sec-butyl acetate industrial chain, solve the problem of acetic acid industry production capacity surplus.At present, be specifically designed to sec-butyl acetate catalytic hydrogenation and prepare the catalyst of sec-butyl alcohol and ethanol and hydrogenation technique has 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 aforementioned techniques object, on the one hand, the invention provides a kind of catalyst of sec-butyl acetate catalytic hydrogenation, the active component element as sec-butyl acetate hydrogenation and adjuvant component element is contained in this catalyst, described active component element is copper and palladium, described adjuvant component element is zinc and zirconium, wherein, also containing alkaline earth element in described catalyst.
Sec-butyl acetate hydrogenation catalyst of the present invention, is characterized in that the mass ratio of copper, palladium element, Zn-ef ficiency, 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, first, the suspension containing solids of sedimentation is obtained after the soluble-salt of adjuvant component element and the soluble-salt of alkaline earth element being contacted in water with precipitating reagent; Secondly, filter after the soluble-salt of active component element and precipitating reagent being contacted in aforementioned suspension and obtain solid sediment.In addition, the subsequent wash of solid sediment, drying and roasting is also comprised.Wherein, described active component element is copper and palladium, and described adjuvant component element is zinc and zirconium.
According to the preparation method of catalyst of the present invention, described wider containing the range of choices 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.
According to the preparation method of catalyst of the present invention, the range of choices of described deposition condition is wider, and for the present invention, preferred described deposition condition comprises: temperature is 40-80 DEG C, and pH value is 7-8 (generally referring to endpoint pH).In the present invention, the condition of precipitation refers to the condition maintained in coprecipitation process, can be maintained the pH value of precipitation process by the charging rate controlling precipitating reagent.
According to the preparation method of catalyst of the present invention, the range of choices of the condition of described drying, the condition of roasting is wider, for the present invention, in order to improve the hydrogenation activity of the catalyst prepared further, the condition of described drying comprises: temperature is 80-120 DEG C, and the time is 4-20h; The condition of roasting comprises: temperature is 350-550 DEG C, and the time is 4-10h.
According to the preparation method of catalyst of the present invention, the precipitating reagent that the routine of prior art uses 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 carried out all under agitation.
Again on the one hand, the invention provides the application of a kind of catalyst of the present invention in sec-butyl acetate hydrogenation reaction.Embody rule method is as follows:
First reduced under reducing atmosphere by catalyst: reduction temperature is 160-240 DEG C, 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 through reduction, 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 DEG C, 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 to have in the reaction of catalyst of the present invention for sec-butyl acetate hydrogenation higher low temperature active and selective by introducing the second active component Pd element in the catalyst of sec-butyl acetate hydrogenation, this is because adding of Pd element makes active component Cu more easily be reduced, change catalyst surface Cu species and distribution situation thereof, the synergy of Pd and Cu improves reactivity and selectivity of product simultaneously.
The present invention by introducing alkaline earth element in the catalyst of sec-butyl acetate hydrogenation, improve decentralization and the stability of copper crystallite on the one hand, adds somewhat to the alkalescence of catalyst on the other hand, avoid dissociating or the generation of the accessory substance such as dehydration of hydrogenation products of raw material, thus improve the selective of hydrogenation products.
The present invention is in the process of preparation sec-butyl acetate hydrogenation catalyst, the method of fractional precipitation is adopted first adjuvant component element and alkaline earth element to be carried out co-precipitation, again the described solid sediment obtained and active component element are precipitated, the catalyst obtained according to method of the present invention is made to have higher activity for sec-butyl acetate hydrogenation reaction, this is because active component is mainly distributed in catalyst coating, reduce the strong interaction of active component and adjuvant component simultaneously, thus provide caused by more hydrogenation activity species.
Catalyst provided by the invention and application are applicable to sec-butyl acetate hydrogenation reaction, are also applicable to the hydrogenation reaction that other contains the raw material of ester.
Catalyst of the present invention has the advantage that low-temperature reactivity is good and selectivity of product is high, and such as, under optimal conditions, when sec-butyl acetate conversion ratio reaches 100%, ethanol selectivity can reach more than 99.5%, and sec-butyl alcohol is selective reaches 100%.
Detailed description of the invention
Further illustrate effect of the present invention by the following examples, but and do not mean that restriction range of application of the present invention.
Embodiment 1
Kaolinite Preparation of Catalyst:
By 189.0 grams of Zn (NO
3)
2, 20.8 grams of ZrCl
4with 50.1 grams of Mg (NO
3)
2metal mixed solution 1 is made into, by (NH by deionized water
4)
2cO
3the aqueous solution and metal mixed solution 1 carry out co-precipitation under 80 DEG C of water-baths, constantly stirring condition, and control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; By 119.3 grams of Cu (NO
3)
2with 4.4 grams of Pd (NO
3)
2metal mixed solution 2 is made into, by (NH by deionized water
4)
2cO
3the aqueous solution and metal mixed solution 2 are 80 DEG C of water-baths, constantly stir and carry out co-precipitation under solids 1 existence condition, and control endpoint pH is 7-8, and finally whole metal ions is solids 2 by co-precipitation; Within 5 hours, namely obtain catalyst A in 450 DEG C of roastings after finally solids 2 being dried 10 hours at 120 DEG C, catalyst and composition thereof are in table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 grams of catalyst A and load that diameters are 12mm, length is in the fixed bed stainless steel reactor of 120cm, reactor upper and lower two ends filling quartz sand, middle loading catalyst, to ensure that catalyst in the flat-temperature zone of reactor (if no special instructions, following examples and comparative example all use this reactor, type of feed is also consistent), in this reactor, first carry out catalyst reduction, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition comprises: temperature is 180 DEG C, and pressure is 1.0MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 10h;
Sec-butyl acetate hydroconversion condition comprises: temperature is 180-230 DEG C, and pressure is 5MPa, and hydrogen ester mol ratio is 100:1, and ester liquid hourly space velocity (LHSV) is 0.5h
-1, reaction result is in table 1.
Embodiment 2
Kaolinite Preparation of Catalyst:
By 80.5 grams of ZnSO
4, 40.4 grams of Zr (NO
3)
4with 30.1 grams of CaCl
2be made into metal mixed solution 1 by deionized water, the NaOH aqueous solution and metal mixed solution 1 are carried out co-precipitation under 60 DEG C of water-baths, constantly stirring condition, and control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; By 68.0 grams of CuSO
4with 1.4 grams of PdCl
2metal mixed solution 2 is made into by deionized water, by the NaOH aqueous solution and metal mixed solution 2 60 DEG C of water-baths, constantly stir and carry out co-precipitation under solids 1 existence condition, control endpoint pH is 7-8, and finally whole metal ions is solids 2 by co-precipitation; Within 6 hours, namely obtain catalyst B in 480 DEG C of roastings after finally solids 2 being dried 15 hours at 100 DEG C, catalyst and composition thereof are in table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 grams of catalyst B to load in fixed bed stainless steel reactor, in this reactor, first carry out catalyst reduction, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition comprises: temperature is 240 DEG C, and pressure is normal pressure, and reducing atmosphere is the hydrogen of argon-dilution, and the recovery time is 4h;
Sec-butyl acetate hydroconversion condition comprises: temperature is 190-250 DEG C, and pressure is 3MPa, and hydrogen ester mol ratio is 60:1, and ester liquid hourly space velocity (LHSV) is 0.6h
-1, reaction result is in table 1.
Embodiment 3
Kaolinite Preparation of Catalyst:
By 136.0 grams of ZnCl
2, 64.3 grams of Zr (SO
4)
2with 5.3 grams of SrCl
2be made into metal mixed solution 1 by deionized water, the KOH aqueous solution and metal mixed solution 1 are carried out co-precipitation under 40 DEG C of water-baths, constantly stirring condition, and control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; By 62.3 grams of CuCl
2with 4.9 grams of PdCl
2metal mixed solution 2 is made into by deionized water, by the KOH aqueous solution and metal mixed solution 2 60 DEG C of water-baths, constantly stir and carry out co-precipitation under solids 1 existence condition, control endpoint pH is 7-8, and finally whole metal ions is solids 2 by co-precipitation; Within 4 hours, namely obtain catalyst C in 550 DEG C of roastings after finally solids 2 being dried 20 hours at 80 DEG C, catalyst and composition thereof are in table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 grams of catalyst C to load in fixed bed stainless steel reactor, in this reactor, first carry out catalyst reduction, 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, catalyst reduction condition comprises: temperature is 160 DEG C, and pressure is 5.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 10h;
Sec-butyl acetate hydroconversion condition comprises: temperature is 180-230 DEG C, and pressure is 3MPa, and hydrogen and sec-butyl acetate mol ratio are 10:1, and ester liquid hourly space velocity (LHSV) is 0.1h
-1, reaction result is in table 1.
Embodiment 4
Kaolinite Preparation of Catalyst:
By 183.0 grams of Zn (CH
3cOO)
2, 13.8 grams of ZrO (NO
3)
2with 82.2 grams of BaCl
2metal mixed solution 1 is made into, by Li by deionized water
2cO
3the aqueous solution and metal mixed solution 1 carry out co-precipitation under 60 DEG C of water-baths, constantly stirring condition, and control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; By 308.1 grams of Cu (CH
3cOO)
2with 2.4 grams of Pd (NO
3)
2metal mixed solution 2 is made into, by Li by deionized water
2cO
3the aqueous solution and metal mixed solution 2 are 80 DEG C of water-baths, constantly stir and carry out co-precipitation under solids 1 existence condition, and control endpoint pH is 7-8, and finally whole metal ions is solids 2 by co-precipitation; Within 10 hours, namely obtain catalyst D in 350 DEG C of roastings after finally solids 2 being dried 4 hours at 120 DEG C, catalyst and composition thereof are in table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 grams of catalyst D to load in fixed bed stainless steel reactor, in this reactor, first carry out catalyst reduction, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition comprises: temperature is 230 DEG C, and pressure is 3.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 5h;
Sec-butyl acetate hydroconversion condition comprises: temperature is 230-260 DEG C, and pressure is 10MPa, and hydrogen ester mol ratio is 200:1, and ester liquid hourly space velocity (LHSV) is 0.8h
-1, reaction result is in table 1.
Embodiment 5
Kaolinite Preparation of Catalyst:
By 169.0 grams of Zn (NO
3)
2, 38.0 grams of Zr (NO
3)
4with 20.6 grams of BeCl
2metal mixed solution 1 is made into, by NaHCO by deionized water
3the aqueous solution and metal mixed solution 1 carry out co-precipitation under 60 DEG C of water-baths, constantly stirring condition, and control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; By 111.7 grams of Cu (HCOO)
2with 0.5 gram of Pd (NO
3)
2metal mixed solution 2 is made into, by NaHCO by deionized water
3the aqueous solution and metal mixed solution 2 are 60 DEG C of water-baths, constantly stir and carry out co-precipitation under solids 1 existence condition, and control endpoint pH is 7-8, and finally whole metal ions is solids 2 by co-precipitation; Within 6 hours, namely obtain catalyst E in 450 DEG C of roastings after finally solids 2 being dried 4 hours at 120 DEG C, catalyst and composition thereof are in table 1.
Catalyst reduction and sec-butyl acetate hydrogenation:
Get 10.0 grams of catalyst E to load in fixed bed stainless steel reactor, in this reactor, first carry out catalyst reduction, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition comprises: temperature is 190 DEG C, and pressure is 2.0MPa, and reducing atmosphere is the hydrogen of nitrogen dilution, and the recovery time is 6h;
Sec-butyl acetate hydroconversion condition comprises: temperature is 210-260 DEG C, and pressure is 5MPa, and hydrogen ester mol ratio is 80:1, and ester liquid hourly space velocity (LHSV) is 0.8h
-1, reaction result is in table 1.
Comparative example 1
According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, do 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 is in table 1.
Comparative example 2
According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, do 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 is in table 1.
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, adjuvant component Zn (NO in preparation process
3)
2, ZrCl
4, Mg (NO
3)
2with active component Cu (NO
3)
2with 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 is in table 1.
Comparative example 4
Outsourcing commercial Cu base ester through hydrogenation catalyst FHE, catalyst reduction and sec-butyl acetate hydrogenation conditions are all with embodiment 1, and reaction result is in table 1.
Table 1
Claims (6)
1. a sec-butyl acetate hydrogenation catalyst, 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 containing alkaline earth element in described catalyst; Described catalyst consists of: the mass ratio of copper, palladium element, Zn-ef ficiency, zr element and alkaline earth element is 100:1-10:60-220:5-70:10-50; The preparation method of described catalyst comprises: under deposition condition, first, obtains the suspension containing solids of sedimentation after the soluble-salt of adjuvant component element and the soluble-salt of alkaline earth element being contacted in water with alkali metal hydroxide; Secondly, filter after the soluble-salt of active component element and alkali metal hydroxide being contacted in aforementioned suspension and obtain solid sediment; Then, the subsequent wash of solid sediment, drying and roasting is also comprised.
2. catalyst according to claim 1, is characterized in that: the mass ratio of copper, palladium element, Zn-ef ficiency, zr element and alkaline earth element is 100:3-5:120-160:20-40:20-40.
3. catalyst according to claim 1, is characterized in that: the condition of described drying comprises: temperature is 80-120 DEG C, and the time is 4-20h; The condition of roasting comprises: temperature is 350-550 DEG C, and the time is 4-10h.
4. an application for the catalyst of sec-butyl acetate hydrogenation, is characterized in that:
First reduced under reducing atmosphere by catalyst described in claim 1 or 2: reduction temperature is 160-240 DEG C, reduction pressure is normal pressure-5MPa, and the recovery time is 4-10h; Then, under the existence of the sec-butyl acetate hydrogenation catalyst through reduction, sec-butyl acetate is contacted with hydrogen.
5. application according to claim 4, is characterized in that: the condition that described sec-butyl acetate contacts with hydrogen is reaction temperature 180-260 DEG C, reaction pressure 3-10MPa, hydrogen and sec-butyl acetate mol ratio 10-200, ester air speed 0.1-0.8h
-1.
6. application according to claim 4, is characterized in that: described reducing atmosphere is the mist of pure hydrogen or hydrogen and inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310103536.1A CN103170352B (en) | 2013-03-28 | 2013-03-28 | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310103536.1A CN103170352B (en) | 2013-03-28 | 2013-03-28 | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103170352A CN103170352A (en) | 2013-06-26 |
| CN103170352B true CN103170352B (en) | 2015-01-14 |
Family
ID=48630798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310103536.1A Active CN103170352B (en) | 2013-03-28 | 2013-03-28 | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103170352B (en) |
Families Citing this family (7)
| 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 hydrogenation production of 1, 4-cyclohexanedimethanol, 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2012121861A (en) * | 2009-10-26 | 2013-12-10 | Селаниз Интернэшнл Корпорейшн | METHODS FOR PRODUCING ETHANOL FROM ACETIC ACID |
| CN102946994B (en) * | 2010-04-21 | 2015-03-18 | 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 |
| CN102146019B (en) * | 2011-02-22 | 2013-05-15 | 湖南长岭石化科技开发有限公司 | Method for preparing alcohols from olefin |
| CN102814184B (en) * | 2012-09-12 | 2014-12-17 | 西北化工研究院 | Catalyst for preparing ethylene glycol by hydrogenating oxalate and preparation method thereof |
-
2013
- 2013-03-28 CN CN201310103536.1A patent/CN103170352B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103170352A (en) | 2013-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103170352B (en) | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof | |
| CN107497437A (en) | One kind is used for CO2It is hydrogenated with ferrum-based catalyst and its application of preparing low-carbon olefins | |
| CN106268852B (en) | A kind of catalyst and the preparation method and application thereof for one-step method from syngas coproduction mixed alcohol and alpha-olefin | |
| CN103611540B (en) | A kind of Catalysts and its preparation method for CO hydrogenation and application | |
| CN103785414B (en) | Hydrogenation of carboxylic acids catalyst, preparation method and application thereof | |
| CN103785384B (en) | A kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation | |
| CN105712840A (en) | Method for producing high-carbon primary alcohols by catalytic conversion of ethanol | |
| CN103599788B (en) | A kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application | |
| CN111514938A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN103785412A (en) | Carboxylic acid hydrogenation catalyst, preparation method and application thereof | |
| CN104785261B (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN107243345A (en) | A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction | |
| CN105032439A (en) | Catalyst for producing sec-butyl alcohol and ethyl alcohol through sec-butyl acetate hydrogenationm, preparation method and application thereof | |
| CN103589446B (en) | A kind of method of iron-based liquid hydrocarbon | |
| CN104959148A (en) | Catalyst for preparing mixed alcohols from synthetic gas and preparation method therefor and application thereof | |
| CN102698764B (en) | Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas | |
| CN102671665A (en) | Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof | |
| CN102744085A (en) | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| US9102583B2 (en) | Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN101992088A (en) | Method for preparing fluidized bed cobalt-based Fisher-Tropsch synthesis catalyst | |
| CN104248953A (en) | Catalyst for preparation of ethanol by acetate hydrogenation and preparation method thereof | |
| CN103586033B (en) | A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application | |
| CN105618062A (en) | Sec-butyl acetate hydrogenation catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 414012 Lu Kou Zhen Chang Lian Long Kou, Yunxi District, Yueyang City, Hunan Province (opposite to Chang Lian hospital) Patentee after: Hunan Changlian New Material Technology Co.,Ltd. Address before: 414012 Yunxi District, Hunan City, Yueyang Province, Changling Patentee before: HUNAN CHANGLING PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |