CN103339093A - Hydrogenation catalyst comprising nickel on carbon - Google Patents
Hydrogenation catalyst comprising nickel on carbon Download PDFInfo
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- 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
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- Prior art keywords
- hydrogenation catalyst
- hydrogenation
- catalyzer
- carrier
- nickel
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- YFKIWUQBRSMPMZ-UHFFFAOYSA-N methane;nickel Chemical compound C.[Ni] YFKIWUQBRSMPMZ-UHFFFAOYSA-N 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 11
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002203 pretreatment Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000006424 Flood reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002303 glucose derivatives Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 241000737241 Cocos Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
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- 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 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.
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 |
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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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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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 |
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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 |
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2012
- 2012-01-18 KR KR1020137022141A patent/KR20140004733A/en not_active Application Discontinuation
- 2012-01-18 CA CA2823676A patent/CA2823676A1/en not_active Abandoned
- 2012-01-18 JP JP2013549918A patent/JP2014507270A/en active Pending
- 2012-01-18 EP EP12739450.0A patent/EP2668148A1/en not_active Withdrawn
- 2012-01-18 WO PCT/IB2012/050243 patent/WO2012101550A1/en active Application Filing
- 2012-01-18 CN CN2012800063705A patent/CN103339093A/en active Pending
Patent Citations (3)
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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)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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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 |
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