CN103339093A - Hydrogenation catalyst comprising nickel on carbon - Google Patents

Hydrogenation catalyst comprising nickel on carbon Download PDF

Info

Publication number
CN103339093A
CN103339093A CN2012800063705A CN201280006370A CN103339093A CN 103339093 A CN103339093 A CN 103339093A CN 2012800063705 A CN2012800063705 A CN 2012800063705A CN 201280006370 A CN201280006370 A CN 201280006370A CN 103339093 A CN103339093 A CN 103339093A
Authority
CN
China
Prior art keywords
hydrogenation catalyst
hydrogenation
catalyzer
carrier
nickel
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.)
Pending
Application number
CN2012800063705A
Other languages
Chinese (zh)
Inventor
A·贝尔斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN103339093A publication Critical patent/CN103339093A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The hydrogenation catalyst comprises from 1 to 50% by weight, based on the total catalyst, of nickel on a carbon support, wherein the hydrogenation catalyst does not comprise any rhenium. Coconut shell carbon is preferably used as support.

Description

The hydrogenation catalyst that comprises nickel at carbon
The present invention relates to a kind ofly comprise the hydrogenation catalyst of nickel at carbon support a kind of method of producing this hydrogenation catalyst and sorbyl alcohol is being hydrogenated to glycol or glucose is hydrogenated to purposes in the sorbyl alcohol.
Prepare chemical feedstocks by renewable resources and just obtaining bigger importance.Therefore, for example can wherein at first obtain starch and then starch be changed into glucose by corn by Maize Production glycol such as propylene glycol and ethylene glycol, change into sorbyl alcohol then, be subsequently converted to glycol such as propylene glycol and ethylene glycol.These are in the preparation of fluoropolymer resin such as urethane or be important source material for the preparation of polymeric crosslinker and other compounds.
Sorbyl alcohol is hydrogenated to glycol such as ethylene glycol and propylene glycol at high temperature and high pressure and also has under the high pH value and carries out in water-bearing media.The inorganic carrier that is usually used in hydrogenation catalyst usually only the short period of time tolerate these conditions (if the words that have), thereby such catalyzer is not suitable for the hydrogenation of sorbyl alcohol.
As selection, proposed to comprise at carbon support the catalyzer of nickel and rhenium.US6,841,085 have described use mainly is hydrogenated to ethylene glycol and propylene glycol at the catalyzer that the coconut palm carbon support has 2.5 weight % nickel and 2.5 weight % rheniums with carbohydrate such as sorbyl alcohol.In the production of this catalyzer, at first the metal salt solution with reactive metal floods this carrier, and is dry and 280 ℃ of reduction 16 hours down then.
Similar approach is described in US7, in 038,094, and the same catalyzer that comprises rhenium and nickel at the coconut palm carbon support that uses wherein.
The purpose of this invention is to provide hydrogenation catalyst, in particular for sorbyl alcohol being hydrogenated to the hydrogenation catalyst of glycol, its withstand high temperatures and high pressure and have the aqueous environment of high pH value and can simply and at an easy rate produce.They should demonstrate the preferential selectivity that obtains propylene glycol and optional ethylene glycol.
According to the present invention, this purpose realizes that at the hydrogenation catalyst that carbon support comprises 1-50 weight % nickel wherein this hydrogenation catalyst does not contain any rhenium based on whole catalyzer by a kind of.
According to the present invention, find to comprise nickel but not comprise rhenium at carbon support to be fit to sorbyl alcohol is hydrogenated to glycol as the hydrogenation catalyst of reactive metal.
This catalyzer can obtain with plain mode, floods with reactive metal because only need.In addition, they are obvious more cheap than known catalysts, use expensive rhenium and use cheap carbon support because they have omitted.
Catalyzer of the present invention does not contain any rhenium.This means that the rhenium and the rhenium that do not comprise industrial significant quantity in this catalyzer are therefore unimportant as reactive metal.
Preferably only comprise nickel as the catalyzer of the present invention of reactive metal.Yet, except nickel, can also have other reactive metals such as molybdenum, vanadium or tin or its mixture.
Catalyzer of the present invention based on whole catalyzer with 1-50 weight %, preferred 5-40 weight %, especially the amount of 10-30 weight % comprises nickel.The ratio of other metals is 0-25 weight %, preferred 0-15 weight %, especially 0-5 weight %.If there is this metalloid, then its minimum is preferably 0.5 weight %.Especially preferably except not having other reactive metals on external this support of the catalyst of nickel, iron, molybdenum, vanadium and/or tin.Particularly preferably in only existing nickel as reactive metal on this support of the catalyst.Particularly, this carbon support only uses nickel as metal impregnation.
According to the present invention, can use any suitable carbon support.For example, can use coconut husk, peridotites or peat coke as carbon support.Can also use synthetic carbon support.Especially preferably use coconut carbon as carrier.
Carbon support can be with the form of being untreated or pre-treatment form for the production of this catalyzer.The pre-treatment of this carbon for example can be carried out by heat, steam, acid or with the chemical mode pre-treatment.Especially preferably carry out water vapour to the steam pre-treatment of coconut carbon.
This carrier can have any suitable particle size.This carrier preferably has 0.5-5mm, the median size of preferred especially 0.75-3.5mm, especially 1-2mm.
The used hydrogenation catalyst of the present invention can be by any appropriate method production.It is usually by flooding this carrier with nickel salt solution, drying is also reduced subsequently and produced then.This reduction is preferably more than 300 ℃, and is preferred especially〉300 ℃ to 700 ℃, particularly 400-600 ℃, especially carry out under 400-500 ℃ the temperature.For example, reduction is handled and can be carried out under about 500 ℃.
The reduction temperature that improves obtains allowing the more high activated catalyst of higher sorb alcohol conversion.Under 500 ℃ hydrogenation temperature, give especially good results.Yet this selectivity of catalyst does not reduce because activity improves.Can carry out aerial stabilization after this reduction, preferably at room temperature carry out.The present invention also provides a kind of catalyzer that can produce by aforesaid method.
It is a kind of by flood this carbon support with nickel salt solution that the present invention also provides, the carrier of dry dipping and the dry carrier of reduction and the method for producing above-mentioned catalyzer under the temperature more than 300 ℃ then subsequently.Preferably use above-mentioned reduction temperature here.
Dipping can be undertaken by any suitable dipping method.Preferably carry out vacuum impregnation.Here can use any suitable nickel salt.Preferably use nickelous nitrate as the aqueous solution.
Dry preferably under 50-150 ℃ temperature and barometric point or preferred decompression, carry out.Dry particularly preferably in carrying out under vacuum or the decompression.
This reduction is preferred comprising in the presence of the gas of free hydrogen, especially carries out in hydrogen atmosphere.
Can carry out the stabilization of nickel-containing catalyst after this reduction, stabilization at room temperature in air for example is to obtain storable stable nickel catalyzator.
Vacuum impregnation causes comprising the nickel catalyzator that very well disperses that average grain size is the nickel crystallite of 2-15nm.Have crystal grain very uniformly here, they in addition obvious agglomeration (if the words that have) does not take place and does not form cluster greatly after using in that the hydrogenation of sorbyl alcohol is medium-term and long-term at this catalyzer.
Typical hydrogenation conditions in the sorbyl alcohol hydrogenation is that temperature is 150-350 ℃, preferred 200-300 ℃, especially about 250 ℃, hydrogen pressure is the 50-300 bar, especially about 150 bar, the concentration of sorbyl alcohol in water are that 10-40 weight %, the especially concentration in water are about 20 weight %, initial pH is 12-13, and this for example sets by adding KOH.
Hydrogenation can also be at US6, and 841,085 and US6, carry out under the reaction conditions described in 479,713.
In order to determine validity and the intensity of catalyzer, sorbyl alcohol hydrogenation is usually 250 ℃ temperature, and the hydrogen pressure of 150 bar is that the sorbitol aqueous solution of 20 weight % carries out to concentration under the pH of 12-13.
The reduction degree of sorbyl alcohol is preferably 50-99%.
Measure the intensity of this catalyzer after about 300 minutes in hydrogenation.For carbon support, especially the coconut carbon carrier does not find that intensity reduces because of hydrogenation.
Therefore, catalyzer of the present invention is preferred for sorbyl alcohol is hydrogenated to glycol, and especially propylene glycol and ethylene glycol have a small amount of glycerine, perhaps is used for glucose is hydrogenated to sorbyl alcohol.
Therefore, the present invention also provides a kind of and has prepared the method for glycol by the hydrogenation sorbyl alcohol, and wherein this hydrogenation is carried out at aforesaid catalyzer.
In addition, the invention provides and a kind ofly prepare the method for sorbyl alcohol by hydrogenated glucose, wherein this hydrogenation is carried out at aforesaid catalyzer.
This hydrogenation is preferably carried out continuously, and wherein this hydrogenation catalyst exists as fixed bed.
The hydrogenation of sorbyl alcohol obtains propylene glycol as principal product and also obtains the significantly more ethylene glycol of a small amount of and even glycerine significantly more in a small amount.Xylitol, butyleneglycol and methyl alcohol and also have lactic acid to form as by product usually.
Form according to the present invention with obvious degree appearance as the methane that under the known catalysts situation, occurs.
Compare with known catalysts, catalyzer of the present invention demonstrates the selectivity of improvement with regard to the preparation of propylene glycol.Particularly, selectivity is very high under the situation of the nickel catalyzator with coconut carbon carrier.
In the situation that significantly is better than the comparative catalyst who additionally comprises rhenium to conversion and the selectivity of propylene glycol and ethylene glycol that contains under the Ni hydrogenation catalysts situation of the present invention.Comprise at carbon support that transformation efficiency and propylene glycol selectivity significantly are better than the situation that comprises the catalyzer of 10 weight % nickel and 1 weight % rhenium at the same carbon carrier under the catalyzer situation of 10 weight % nickel.
Hydrogenated glucose with the method for preparing sorbyl alcohol in, this reaction is preferably at 50-250 ℃, preferred especially 90-140 ℃ temperature, the 30-250 bar, the pressure of preferred especially 60-150 bar and the glucose concn in preferred D/W are 30-70 weight %, carry out under the preferred especially 40-60 weight %.In continuation method, air speed is preferably 0.15-2l/lh.
The adding of alkali is also unnecessary usually.After about 300 hours, the intensity of this catalyzer in fixed bed does not change.
Compare with known catalysts, catalyzer of the present invention demonstrates improved selectivity and activity with regard to the sorbyl alcohol preparation.Particularly, selectivity is very high under the situation of nickel catalyzator and coconut carbon carrier.
The present invention is illustrated by the following example.
Embodiment 1: the production of catalyzer
Carbon extrudate or particulate state carbon are used as raw material.Yet, the coconut carbon that preferred use can be obtained with trade name SHIRASAGI C2X8/12 by Japan EnviroChemicals Ltd..The bulk density of this carbon is that about 0.5g/ml and average particle size particle size are 1.8mm.
For example at first producing, nickel concentration is the aqueous solution that comprises nickelous nitrate in deionized water of 14.4 weight %.For example, with the 53.3g Ni (NO in 22.0g water 3) 2.6H 2O is used for dipping 50g carbon extrudate.
Carry out vacuum impregnation as dipping.This carbon support was kept under reduced pressure 30 minutes, then with the above-mentioned solution spray dipping that comprises nickelous nitrate.Heating and the dry carrier that floods then.Destroy vacuum then and pass air into.
In order to reduce the support of the catalyst of dipping, it is heated to the reduction temperature of 410 ℃ or 450 ℃ or 500 ℃ with the heating rate of 60 ℃/h under nitrogen (100ml/h).Slowly introduce hydrogen then.After adding 100% hydrogen, this catalyzer was kept under this temperature 4 hours.Under nitrogen (100ml/h), be quickly cooled to 50 ℃ then.Slowly allow air admission to carry out the stabilization of this catalyzer then.

Claims (12)

1. one kind comprises the hydrogenation catalyst of 1-50 weight % nickel based on whole catalyzer at carbon support, and wherein said hydrogenation catalyst does not comprise any rhenium.
2. according to the hydrogenation catalyst of claim 1, wherein coconut carbon is used as carrier.
3. according to the hydrogenation catalyst of claim 1 or 2, wherein said carbon support is by warm, steam, acid or with the chemical mode pre-treatment.
4. according to each hydrogenation catalyst among the claim 1-3, wherein said carrier has the median size of 0.5-5mm.
5. according to each hydrogenation catalyst among the claim 1-4, wherein said carrier is with the nickel salt solution dipping, and is dry and reduce under the temperature more than 300 ℃ then.
6. a method of producing according to each hydrogenation catalyst among the claim 1-5 comprises with nickel salt solution and floods described carbon support, the carrier of dry dipping and the dry carrier of reduction under the temperature more than 300 ℃ then subsequently.
7. according to the method for claim 6, wherein said reduction is carried out under 400-600 ℃ temperature.
8. according to the method for claim 6 or 7, wherein said carrier before dipping by heat, steam, acid or with the chemical mode pre-treatment.
9. sorbyl alcohol is being hydrogenated to glycol or glucose is being hydrogenated to purposes in the sorbyl alcohol according to each hydrogenation catalyst among the claim 1-5.
10. one kind prepares the method for glycol by the hydrogenation sorbyl alcohol, and wherein said hydrogenation each catalyzer in according to claim 1-5 carries out.
11. one kind prepares the method for sorbyl alcohol by hydrogenated glucose, wherein said hydrogenation each catalyzer in according to claim 1-5 carries out.
12. according to the method for claim 10 or 11, wherein said hydrogenation is carried out continuously and described hydrogenation catalyst exists as fixed bed.
CN2012800063705A 2011-01-24 2012-01-18 Hydrogenation catalyst comprising nickel on carbon Pending CN103339093A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11151797 2011-01-24
EP11151797.5 2011-01-24
PCT/IB2012/050243 WO2012101550A1 (en) 2011-01-24 2012-01-18 Hydrogenation catalyst comprising nickel on carbon

Publications (1)

Publication Number Publication Date
CN103339093A true CN103339093A (en) 2013-10-02

Family

ID=46580264

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012800063705A Pending CN103339093A (en) 2011-01-24 2012-01-18 Hydrogenation catalyst comprising nickel on carbon

Country Status (6)

Country Link
EP (1) EP2668148A1 (en)
JP (1) JP2014507270A (en)
KR (1) KR20140004733A (en)
CN (1) CN103339093A (en)
CA (1) CA2823676A1 (en)
WO (1) WO2012101550A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557452A (en) * 2015-01-04 2015-04-29 南京工业大学 Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst
CN109789391A (en) * 2016-09-30 2019-05-21 赢创德固赛有限公司 Prepare the method and catalyst of 1,4- butanediol
CN110721686A (en) * 2019-09-27 2020-01-24 中国科学院广州能源研究所 Catalytic cracking catalyst using peat carbon base as carrier
CN110813297A (en) * 2019-10-15 2020-02-21 厦门大学 Synthesis method of sugar alcohol

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1023643B1 (en) 2016-03-21 2017-06-01 Yun NV VAGINAL PREPARATIONS FOR MAINTENANCE AND / OR REPAIR OF A HEALTHY FEMALE MICROBIOTA
EP3300798A1 (en) 2016-09-30 2018-04-04 Evonik Degussa GmbH Catalyst fixed bed containing metal foam body
EP3752477B1 (en) 2018-02-14 2024-05-22 Evonik Operations GmbH Method for the preparation of c3-c12-alcohols by catalytic hydrogenation of the corresponding aldehydes
KR20210038540A (en) 2019-09-25 2021-04-07 에보닉 오퍼레이션스 게엠베하 Catalytic reactor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119952A1 (en) * 2001-10-23 2003-06-26 Werpy Todd A. Hydrogenolysis of 6-carbon sugars and other organic compounds
US20040064003A1 (en) * 2001-10-23 2004-04-01 Werpy Todd A. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol
CN101735014A (en) * 2008-11-26 2010-06-16 中国科学院大连化学物理研究所 Method for preparing ethanediol from polyhydroxy compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0708416A2 (en) * 2006-03-01 2011-05-31 Univ Hokkaido Nat Univ Corp catalyst for cellulose hydrolysis and / or reduction of hydrolysis products, and method of production of sugar alcohols
CN101747150B (en) * 2008-12-11 2014-09-03 中科合成油技术有限公司 Method for producing 1,3-propanediol
CN102190562B (en) * 2010-03-17 2014-03-05 中国科学院大连化学物理研究所 Method for preparing ethylene glycol from polyols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119952A1 (en) * 2001-10-23 2003-06-26 Werpy Todd A. Hydrogenolysis of 6-carbon sugars and other organic compounds
US20040064003A1 (en) * 2001-10-23 2004-04-01 Werpy Todd A. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol
CN101735014A (en) * 2008-11-26 2010-06-16 中国科学院大连化学物理研究所 Method for preparing ethanediol from polyhydroxy compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557452A (en) * 2015-01-04 2015-04-29 南京工业大学 Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst
CN109789391A (en) * 2016-09-30 2019-05-21 赢创德固赛有限公司 Prepare the method and catalyst of 1,4- butanediol
CN110721686A (en) * 2019-09-27 2020-01-24 中国科学院广州能源研究所 Catalytic cracking catalyst using peat carbon base as carrier
CN110721686B (en) * 2019-09-27 2022-10-14 中国科学院广州能源研究所 Catalytic cracking catalyst using peat carbon as carrier
CN110813297A (en) * 2019-10-15 2020-02-21 厦门大学 Synthesis method of sugar alcohol
CN110813297B (en) * 2019-10-15 2021-04-30 厦门大学 Synthesis method of sugar alcohol

Also Published As

Publication number Publication date
JP2014507270A (en) 2014-03-27
CA2823676A1 (en) 2012-08-02
KR20140004733A (en) 2014-01-13
WO2012101550A1 (en) 2012-08-02
EP2668148A1 (en) 2013-12-04

Similar Documents

Publication Publication Date Title
CN103339093A (en) Hydrogenation catalyst comprising nickel on carbon
CN106179440B (en) N doping multi-stage porous charcoal and its preparation method and application
RU2528389C2 (en) Mesoporous carbon supported tunsten-carbide catalysts, production and use thereof
CN109382104B (en) Method and catalyst for preparing ethanol from lignocellulose biomass in one step
JP6893270B2 (en) Methods of using this to produce improved copper-containing multi-element metal catalysts and bio-based 1,2-propanediols.
CN102302934B (en) Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst
CN102688768B (en) Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof
CN102502598B (en) Catalytic graphitization method for wood powder
KR20210059228A (en) Supported Copper Catalyst and Selective Hydrogenation of Furan-based Compounds Using the Same
CN103785396B (en) A kind of preparation method of catalyst for heavy oil hydrogenation demetal
CN104072335B (en) A kind of cellulose catalytic converts dihydroxylic alcohols processed, hexahydroxylic alcohols and the method for gamma-valerolactone
CN102974382A (en) Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof
CN108623436A (en) A kind of one kettle way conversion cellulose is the method for bio-ethanol
Pothu et al. Sustainable conversion of biodiesel-waste glycerol to acrolein over Pd-modified mesoporous catalysts
CN102125852A (en) Preparation method of methanol synthesis catalyst
Longo et al. Waste biomasses as precursors of catalytic supports in benzaldehyde hydrogenation
CN109046409A (en) A kind of preparation method of phosphatization cobalt-molybdenum disulfide nano sheet@carbon nanotube
CN115318296B (en) High-dispersion film-shaped carbon-coated nickel catalyst and preparation method and application thereof
CN103801290A (en) Precious metal methanation catalyst prepared by using solution combustion method and preparation method and applications thereof
CN103801299A (en) Preparation method of catalyst for syngas preparation by methane partial oxidation
CN109603837A (en) A kind of preparation method of the Cu/Ce/Co catalyst for furfural liquid-phase hydrogenatin
CN110013868B (en) Tungsten phosphide catalyst for preparing 2,3,3, 3-tetrafluoropropene through selective hydrogenation dechlorination
CN104862023B (en) A kind of method of chemical catalysis production biological fuel gas
US20140194541A1 (en) Catalyst for c2 oxygenate synthesis, device for manufacturing c2 oxygenate, and method for manufacturing c2 oxygenate
CN101347731A (en) Platelet-carbon nanofibers supported ruthenium catalyst and preparation method and use thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20131002

RJ01 Rejection of invention patent application after publication