[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CA2823676A1 - Hydrogenation catalyst comprising nickel on carbon - Google Patents

Hydrogenation catalyst comprising nickel on carbon Download PDF

Info

Publication number
CA2823676A1
CA2823676A1 CA2823676A CA2823676A CA2823676A1 CA 2823676 A1 CA2823676 A1 CA 2823676A1 CA 2823676 A CA2823676 A CA 2823676A CA 2823676 A CA2823676 A CA 2823676A CA 2823676 A1 CA2823676 A1 CA 2823676A1
Authority
CA
Canada
Prior art keywords
hydrogenation
support
catalyst
nickel
carbon
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.)
Abandoned
Application number
CA2823676A
Other languages
French (fr)
Inventor
Annemarie BEERS
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 CA2823676A1 publication Critical patent/CA2823676A1/en
Abandoned 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
    • 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
    • B01J35/45—Nanoparticles
    • 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
    • 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

Hydrogenation catalyst comprising nickel on carbon Description The invention relates to a hydrogenation catalyst comprising nickel on a carbon support, a process for producing the hydrogenation catalyst and its use for the hydrogenation of sorbitol to glycols or the hydrogenation of glucose to sorbitol.
The preparation of chemical starting materials from renewable sources is gaining ever greater importance. Thus, for example, glycols such as propylene glycol and ethylene glycol can be produced from maize, with starch firstly being obtained from the maize and subsequently being converted into glucose, then sorbitol and subsequently glycols such as propylene glycol and ethylene glycol. These are important starting materials in the preparation of polymer resins such as polyurethanes or for the preparation of polymer crosslinkers and other chemical compounds.
The hydrogenation of sorbitol to glycols such as ethylene glycol and propylene glycol is carried out at high temperatures and pressures and also high pH values in an aqueous medium. Inorganic supports customarily used for hydrogenation catalysts generally withstand these conditions for only a short time, if at all, so that such catalysts are unsuitable for the hydrogenation of sorbitol.
As an alternative, catalysts comprising nickel and rhenium on a carbon support have been proposed. US 6,841,085 describes the hydrogenation of sugars such as sorbitol to predominantly ethylene glycol and propylene glycol using a catalyst having
2.5% by weight of nickel and 2.5% by weight of rhenium on a coconut carbon support. In the production of the catalyst, the support is firstly impregnated with metal salt solutions of the active metals, subsequently dried and reduced at 280 C for 16 hours.
A similar process is described in US 7,038,094, in which a catalyst comprising rhenium and nickel on a coconut carbon support is likewise used.
It is an object of the present invention to provide hydrogenation catalysts, in particular for the hydrogenation of sorbitol to glycols, which withstand high temperatures and pressures and an aqueous environment having high pH values and can be produced simply and inexpensively. They should display preferential selectivity to propylene glycol and optionally ethylene glycol.
The object is achieved according to the invention by a hydrogenation catalyst comprising 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.

It has been found according to the invention that hydrogenation catalysts comprising nickel but no rhenium as active metal on a carbon support are suitable for the hydrogenation of sorbitol to glycols.
The catalysts can be obtained in a simple manner since only impregnation with an active metal is necessary. In addition, they are significantly cheaper than known catalysts since they dispense with the use of costly rhenium and use inexpensive carbon supports.
The catalyst of the invention does not contain any rhenium. This means that no technically effective amounts of rhenium are comprised in the catalyst and rhenium thus has no importance as active metal.
Preference is given to catalysts according to the invention which comprise only nickel as active metal. However, it is also possible for further active metals such as molybdenum, vanadium or tin or mixtures thereof to be present in addition to nickel.
The catalyst of the invention comprises nickel in an amount of from 1 to 50%
by weight, preferably from 5 to 40% by weight, in particular from 10 to 30% by weight, based on the total catalyst. The proportion of further metals is from 0 to 25% by weight, preferably from 0 to 15% by weight, in particular from 0 to 5% by weight. If such metals are present, their minimum amount is preferably 0.5% by weight. Particular preference is given to no further active metals apart from nickel, iron, molybdenum, vanadium and/or tin being present on the catalyst support. Particular preference is given to only nickel being present as active metal on the catalyst support. In particular, the carbon support is impregnated only with nickel as metal.
According to the invention, any suitable carbon supports can be used. For example, it is possible to use coconut shells, olive stones or peat charcoal as carbon support. It is also possible to use synthetic carbon supports. Particular preference is given to using coconut shell carbon as support.
The carbon support can be used in untreated form or pretreated form for producing the catalyst. Pretreatment of the carbon can be carried out, for example, by means of heat, steam, acids or chemical pretreatment. A steam pretreatment of the coconut shell carbon with water vapor is particularly preferably carried out.
3 The support can have any suitable particle size. The support preferably has an average particle diameter in the range from 0.5 to 5 mm, particularly preferably from 0.75 to 3.5 mm, in particular from 1 to 2 mm.
The hydrogenation catalyst used according to the invention can be produced by any suitable processes. It is usually produced by impregnation of the support with a nickel salt solution, subsequent drying and subsequent reduction. The reduction is preferably carried out at a temperature above 300 C, particularly preferably in the range from > 300 C to 700 C, in particular in the range from 400 to 600 C, especially in the range from 400 to 500 C. For example, the reduction treatment can be carried out at about 500 C.
An increased reduction temperature leads to more active catalysts which allow a higher sorbitol conversion. Particularly good results are obtained at a hydrogenation temperature of 500 C. However, the selectivity of the catalyst is not reduced by the increased activity. The reduction can be followed by stabilization in air, preferably at room temperature. The invention also provides a catalyst which can be produced by the above process.
The invention also provides a process for producing the above catalyst by impregnation of the carbon support with a nickel salt solution, subsequent drying of the impregnated support and subsequent reduction of the dried support at a temperature above 300 C.
The abovementioned reduction temperatures are preferably employed here.
Impregnation can be carried out by any suitable impregnation methods.
Preference is given to carrying out vacuum impregnation. Any suitable nickel salts can be employed here. Preference is given to using nickel nitrate as aqueous solution.
Drying is preferably carried out at a temperature in the range from 50 to 150 C and atmospheric pressure or preferably under reduced pressure. Drying is particularly preferably carried out under vacuum or reduced pressure.
The reduction is preferably carried out in the presence of a gas comprising free hydrogen, in particular in a hydrogen atmosphere.
The reduction can be followed by stabilization of the nickel-comprising catalyst, for example in air at room temperature, in order to obtain a storable, stable nickel catalyst.
Vacuum impregnation leads to a very well dispersed nickel catalyst comprising nickel crystallites having an average crystallite size in the range from 2 to 15 nm.
Very
4 uniform crystallites which do not undergo appreciable agglomeration, if any, and do not form relatively large clusters even after prolonged use of the catalyst in the hydrogenation of sorbitol are present here.
Typical hydrogenation conditions in the hydrogenation of sorbitol are a temperature in the range from 150 to 350 C, preferably from 200 to 300 C, in particular about 250 C, a hydrogen pressure in the range from 50 to 300 bar, in particular about 150 bar, a sorbitol concentration of from 10 to 40% by weight in water, in particular about 20% by weight in water, an initial pH in the range from 12 to 13, for example set by addition of KOH.
The hydrogenation can also be carried out under the reaction conditions as are described in US 6,841,085 and US 6,479,713.
To determine the effectiveness and strength of the catalysts, the sorbitol hydrogenation is generally carried out at a temperature of 250 C, a hydrogen pressure of 150 bar, a pH of from 12 to 13 on a 20% strength by weight aqueous sorbitol solution.
The degree of reduction of the sorbitol is preferably in the range from 50 to 99%.
After hydrogenation for a period of about 300 minutes, the strength of the catalyst is determined. No reduction in the strength as a result of the hydrogenation is found for the carbon supports, in particular the coconut shell carbon supports.
The catalysts of the invention are thus preferably used for the hydrogenation of sorbitol to glycols, in particular propylene glycol and ethylene glycol, with small amounts of glycerol, or for the hydrogenation of glucose to sorbitol.
The invention therefore also provides a process for preparing glycols by hydrogenation of sorbitol, in which the hydrogenation is carried out over a catalyst as described above.
In addition, the invention provides a process for preparing sorbitol by hydrogenation of glucose, wherein the hydrogenation is carried out over a catalyst as described above.
The hydrogenation is preferably carried out continuously, with the hydrogenation catalyst being present as a fixed bed.
The hydrogenation of sorbitol gives propylene glycol as main product, and also ethylene glycol in a significantly smaller amount and even significantly smaller amounts of glycerol. Xylitol, butanediol and methanol and also lactic acid are typically formed as by-products.
The formation of methane, as occurs in the case of the known catalysts, does not occur
5 to an appreciable extent according to the invention.
Compared to known catalysts, the catalysts of the invention display improved selectivity in respect of the preparation of propylene glycol. In particular, the selectivity is very high in the case of nickel catalysts having coconut shell carbon supports.
Conversion and selectivity to propylene glycol and ethylene glycol are significantly better in the case of the nickel-comprising hydrogenation catalyst of the invention than in the case of a comparative catalyst which additionally comprises rhenium.
Both the conversion and the propylene glycol selectivity were significantly better in the case of a catalyst comprising 10% by weight of nickel on a carbon support than in the case of a catalyst comprising 10% by weight of nickel and 1% by weight of rhenium on the same carbon support.
In the process for the hydrogenation of glucose for preparing sorbitol, the reaction is preferably carried out at a temperature in the range from 50 to 250 C, particularly preferably from 90 to 140 C, a pressure in the range from 30 to 250 bar, particularly preferably from 60 to 150 bar, and a glucose concentration in the preferably aqueous glucose solution in the range from 30 to 70% by weight, particularly preferably from 40 to 60% by weight. In a continuous process, the space velocity is preferably from 0.15 to 2 I/I- h.
An addition of base is typically not necessary. After about 300 hours, the strength of the catalyst in the fixed bed had not changed.
Compared to known catalysts, the catalysts of the invention display improved selectivity and activity in respect of the preparation of sorbitol. In particular, the selectivity is very high in the case of nickel catalysts and coconut shell carbon supports.
The invention is illustrated by the following example.
Example 1: Production of the catalyst Carbon extrudates or granulated carbon were used as starting materials.
However, coconut shell carbon as can be obtained from Japan EnviroChemicals Ltd. under the
6 trade name SHIRASAGI C2X8/12 was preferably used. This carbon has a bulk density of about 0.5 g/ml and an average particle size of 1.8 mm.
An aqueous solution comprising nickel nitrate in deionized water having, for example, a nickel concentration of 14.4% by weight was firstly produced. For example, 53.3 g of Ni(NO3)2.6 H20 in 22.0 g of water was used for the impregnation of 50 g of carbon extrudates.
A vacuum impregnation was carried out as impregnation. The carbon support was maintained under reduced pressure for 30 minutes, after which it was spray impregnated with the above solution comprising nickel nitrate. Heating and drying of the impregnated support followed. The vacuum was then broken and air was allowed to flow in.
To reduce the impregnated catalyst support, this was heated to a reduction temperature of 410 C or 450 C or 500 C at a heating rate of 60 C/h under nitrogen (100 ml/h). Hydrogen was then slowly introduced. After addition of 100% of the hydrogen, the catalyst was maintained at this temperature for 4 hours. It was then quickly cooled to 50 C under nitrogen (100 ml/h). Air was then slowly admitted in order to carry out stabilization of the catalyst.

Claims (11)

As enclosed to IPRP
Claims
1. A hydrogenation catalyst comprising 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, wherein the support has been impregnated with a nickel salt solution, then dried and reduced at a temperature above 300°C.
2. The hydrogenation catalyst according to claim 1, wherein coconut shell carbon is used as support.
3. The hydrogenation catalyst according to claim 1 or 2, wherein the carbon support is pretreated by means of heat, steam, acids or chemically.
4. The hydrogenation catalyst according to any of claims 1 to 3, wherein the support has an average particle diameter in the range from 0.5 to 5 mm.
A process for producing a hydrogenation catalyst according to any of claims 1 to 4 by impregnation of the carbon support with a nickel salt solution, subsequent drying of the impregnated support and subsequent reduction of the dried support at a temperature above 300°C.
6. The process according to claim 5, wherein the reduction is carried out at a temperature of from 400 to 600°C.
7. The process according to claim 5 or 6, wherein the support is pretreated by means of heat, steam, acids or chemically before impregnation
8. The use of a hydrogenation catalyst according to any of claims 1 to 4 for the hydrogenation of sorbitol to glycols or the hydrogenation of glucose to sorbitol.
9. A process for preparing glycols by hydrogenation of sorbitol, wherein the hydrogenation is carried out over a catalyst according to any of claims 1 to 4.
10. A process for preparing sorbitol by hydrogenation of glucose, wherein the hydrogenation is carried out over a catalyst according to any of claims 1 to 4.
11. The process according to claim 9 or 10, wherein the hydrogenation is carried out continuously and the hydrogenation catalyst is present as a fixed bed.
CA2823676A 2011-01-24 2012-01-18 Hydrogenation catalyst comprising nickel on carbon Abandoned CA2823676A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11151797.5 2011-01-24
EP11151797 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
CA2823676A1 true CA2823676A1 (en) 2012-08-02

Family

ID=46580264

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2823676A Abandoned CA2823676A1 (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
US11090637B2 (en) 2016-09-30 2021-08-17 Evonik Operations Gmbh Fixed catalyst bed comprising metal foam bodies
US11260375B2 (en) 2016-09-30 2022-03-01 Evonik Operations Gmbh Process and catalyst for preparing 1,4-butanediol
US11401224B2 (en) 2018-02-14 2022-08-02 Evonik Operations Gmbh Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes
US11819832B2 (en) 2019-09-25 2023-11-21 Evonik Operations Gmbh Catalytic reactor

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557452B (en) * 2015-01-04 2017-02-22 南京工业大学 Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst
BE1023643B1 (en) 2016-03-21 2017-06-01 Yun NV VAGINAL PREPARATIONS FOR MAINTENANCE AND / OR REPAIR OF A HEALTHY FEMALE MICROBIOTA
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
CN110813297B (en) * 2019-10-15 2021-04-30 厦门大学 A kind of synthetic method of sugar alcohol

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6479713B1 (en) * 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
US6841085B2 (en) * 2001-10-23 2005-01-11 Battelle Memorial Institute Hydrogenolysis of 6-carbon sugars and other organic compounds
WO2007100052A1 (en) * 2006-03-01 2007-09-07 National University Corporation Hokkaido University Catalyst for hydrolysis of cellulose and/or reduction of hydrolysis product thereof, and method for producing sugar alcohol from cellulose
CN101735014B (en) * 2008-11-26 2013-07-24 中国科学院大连化学物理研究所 Method for preparing ethanediol from polyhydroxy compounds
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 A kind of method of polyhydroxy compound preparation ethylene glycol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11090637B2 (en) 2016-09-30 2021-08-17 Evonik Operations Gmbh Fixed catalyst bed comprising metal foam bodies
US11260375B2 (en) 2016-09-30 2022-03-01 Evonik Operations Gmbh Process and catalyst for preparing 1,4-butanediol
US11401224B2 (en) 2018-02-14 2022-08-02 Evonik Operations Gmbh Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes
US11819832B2 (en) 2019-09-25 2023-11-21 Evonik Operations Gmbh Catalytic reactor

Also Published As

Publication number Publication date
EP2668148A1 (en) 2013-12-04
CN103339093A (en) 2013-10-02
JP2014507270A (en) 2014-03-27
KR20140004733A (en) 2014-01-13
WO2012101550A1 (en) 2012-08-02

Similar Documents

Publication Publication Date Title
CA2823676A1 (en) Hydrogenation catalyst comprising nickel on carbon
US20120178974A1 (en) Mesoporous carbon supported tungsten carbide catalysts, preparation and applications thereof
JPS60501104A (en) Gas phase hydrogenation of esters
CN104475143B (en) Nitrogen-doped activated carbon catalyst and application thereof
Priya et al. Catalytic performance of Pt/AlPO 4 catalysts for selective hydrogenolysis of glycerol to 1, 3-propanediol in the vapour phase
KR20160010151A (en) Catalyst for decomposition and regeneration of formic acid and method for preparing the same
CN108409692B (en) Method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation with sulfur-doped carbon material-loaded ruthenium catalyst
CN104289254B (en) Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst
CN105601494B (en) A kind of method of nanometer of propane diols of copper catalysis 1,2 oxidation
JP2019526588A (en) Method for producing 1,3-cyclohexanedimethanol
CN109608307B (en) Method for preparing 1, 3-propylene glycol by glycerol hydrogenolysis and reaction system thereof
Wang et al. Significant effect of Ca modification on improving catalytic stability of Cu-catalyst in gas-phase furfural hydrogenation to furfuralcohol
US20120190899A1 (en) Hydrogenation catalyst comprising nickel on carbon
CN111774089A (en) A kind of glycerol hydrodeoxygenation catalyst and its preparation method and application
JP3788172B2 (en) Method for producing ammonia synthesis catalyst and method for ammonia synthesis
JP2016185891A (en) Production method of carbon monoxide
KR101805086B1 (en) Method for preparing catalyst for glycerin dehydration, catalyst for glycerin dehydration, and preparing method of acrolein
Bhattacharyya et al. Catalytic synthesis of lactic acid from acetaldehyde, carbon monoxide, and water
CN101502801B (en) Preparation method of active carbon supported nickel catalyst for synthesizing ethylformic acid
JP7403504B2 (en) Method for producing 1-chloro-2,2-difluoroethylene
KR102724061B1 (en) Catalyst for preparing 1,3-cyclopentanediol, method for preparing 1,3-cyclopentanediol using the same, and 1,3-cyclopentanediol prepared by using the same
CN112295569A (en) Catalyst for preparing aniline by one-step ammoniation of benzene and preparation method thereof
KR102697807B1 (en) Ruthenium catalyst for decomposition reaction of ammonia, method of manufacturing the ruthenium catalyst, and method of producing hydrogen from ammonia using the ruthenium catalyst
JP4359447B2 (en) Method for producing monohydroxyacetone
CN116037170B (en) A catalyst for preparing 1,1,2-trifluoroethylene and a method for preparing 1,1,2-trifluoroethylene

Legal Events

Date Code Title Description
FZDE Discontinued

Effective date: 20180118