CN106040246A - Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol - Google Patents
Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol Download PDFInfo
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- CN106040246A CN106040246A CN201610482336.5A CN201610482336A CN106040246A CN 106040246 A CN106040246 A CN 106040246A CN 201610482336 A CN201610482336 A CN 201610482336A CN 106040246 A CN106040246 A CN 106040246A
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- Prior art keywords
- nickel
- butynediols
- hydrogen
- catalyst
- nitrae
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 7
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title abstract 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 150000002431 hydrogen Chemical class 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000006073 displacement reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 241001502050 Acis Species 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001201 calcium disodium ethylene diamine tetra-acetate Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000002083 enediols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- -1 zinc salt Chemical class 0.000 description 1
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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/40—
-
- B01J35/615—
-
- B01J35/633—
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a nickel-based catalyst and a preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol. The nickel-based catalyst is prepared by using a sol-gel method and contains active components including metal nickel, metal copper and metal zinc, wherein silicon dioxide is taken as a carrier. The preparation method specifically comprises the following steps: dissolving a metal inorganic salt of active components in water so as to prepare a solution, further adding a silicon source tetraethyl orthosilicate, solvent alcohol and hydrolytic reagent acid so as to obtain sol-gel at certain temperature, drying and roasting so as to obtain a catalyst precursor, and reducing the precursor in the presence of hydrogen, thereby obtaining the 1,4-butynediol selective hydrogenation catalyst. The nickel-based catalyst contains high-dispersion, nano-grade and relatively low-cost active metal monomers as the active components, the surface specific area is as high as 300-500m<2>/g, the nickel-based catalyst is used in the reaction process of synthesizing 1,4-butylene glycol from 1,4-butynediol through selective hydrogenation, the reaction conversion rate is greater than 95%, and the selectivity is greater than 96%.
Description
Technical field
The invention belongs to Application in Chemical Engineering field, relate to one and prepared Isosorbide-5-Nitrae-butylene two by Isosorbide-5-Nitrae-butynediols selective hydrogenation
The catalyst of alcohol and using method thereof.
Background technology
Isosorbide-5-Nitrae-butylene glycol is a kind of colourless liquid, mainly can be as intermediate in pesticide, field of medicaments, Shao Liangyong
In production processes of polyalcohol.As being used for synthesizing organochlorine insecticide 5a,6,9,9a-hexahydro-6,9-methano-2,4 in pesticide, for synthetic vitamin in medicine
B6 etc..Current industrial production 1,4-butylene glycol is mainly prepared by 1,4-butynediols selective hydrogenation.
Generally hydrogenation catalyst main active component is noble metal cobalt, ruthenium, rhodium, palladium, platinum and metallic nickel etc., and carrier is usually
Aluminium oxide, silicon oxide, activated carbon etc..But, in the course of reaction for alkynes selective hydrogenation alkene, the alkene ratio of generation
Alkynes is easier to absorption and on a catalyst and is difficult to desorption, therefore causes hydrogenation products mainly based on saturated alkane, and alkene is received
Rate is the lowest.
In order to obtain alkene, research worker has carried out numerous studies.Found by research, use poisonous agent to poison activity group
Point, product can be rested on alkene.As added the quinoline (DE 115238) of trace, at palladium/oxygen in using palladium/barium sulfate
Change Al catalysts to add carbon monoxide (DE 2619660), in palladium/aluminium oxide, add copper (GB 832142), at palladium/aluminium oxide
Middle addition copper, zinc and silver (CN95193955.6), in palladium/calcium carbonate, add lead (Org.Synth.1966,48:89-92) etc..
Although catalyst provided above in use shows higher hydrogenation selectivity, but due to catalyst activity
Component is precious metal palladium, and therefore catalyst holistic cost is costly.Meanwhile, active component palladium is immobilized in carrier surface, therefore
Unavoidably there is the loss of active component, cause catalyst reusability poor, be further exacerbated by production cost.
Summary of the invention
It is an object of the invention to provide a kind of high activity, high selective nickel-base catalyst, to replace your conventional gold
Metal catalyst, is applied to Isosorbide-5-Nitrae-butynediols selective hydrogenation and prepares in Isosorbide-5-Nitrae-butylene glycol course of reaction.Use the present invention's
Thering is provided the selective hydrocatalyst that preparation method prepares, active height, good selective, especially with low-priced gold
Belonging to nickel replaces precious metal palladium as active component, and therefore catalyst holistic cost is greatly lowered, and is more suitable for the big rule of industrialization
Mould produces in 1,4-butylene glycol course of reaction.
It is known that sol-gel process is to be prepared through hydrolysis, polycondensation reaction by metallic compound or coordination compound
The gel-like compound with three dimensional structure.And the catalyst using sol-gel process to prepare has higher ratio table
The advantages such as the controllability of area, high degree of dispersion, process and pore structure, prepared by its activity and selectivity significantly larger than traditional method
Catalyst.
Catalyst provided by the present invention uses sol-gel process to prepare, and specific surface area is up to 300～500m2/ g,
Active component nickel particle granules size is 4～10nm, therefore shows stronger activity in course of reaction.Meanwhile, in order to more
Good promotes that the alkene generated in alkynes selective hydrogenation process is desorbed from catalyst surface, it is to avoid continue to be hydrogenated to saturated
Alkane, therefore adds again metallic copper and metallic zinc component in catalyst provided by the present invention, by three kinds of metallic nickels, copper,
Electronic effect between zinc, reduces the energy of adsorption of alkene, thus promotes the selectivity of intermediate product alkene.It is embodied in,
Under reaction temperature 50～80 DEG C, reaction pressure 0.5～1.5Mpa, Isosorbide-5-Nitrae-butynediols conversion ratio up to more than 95%, Isosorbide-5-Nitrae-fourth
Enediol selectivity is up to 96%.
The technical solution adopted in the present invention is as follows:
A kind of by catalyst of Isosorbide-5-Nitrae-butynediols selective hydrogenation synthesis Isosorbide-5-Nitrae-butylene glycol and preparation method thereof, it is special
Levy and be that this catalyst uses sol-gel process to prepare.Concrete preparation process is as follows:
(1) nickel, copper, the inorganic salt of zinc are dissolved in deionized water, form solution A；
(2) positive for silicon source esters of silicon acis, solvent alcohol and hydrolytic reagent acid are mixed, form solution B；
(3) after solution A being added dropwise in solution B, and it is stirred at room temperature 1～24 hour；
(4) room temperature stands 6～72 hours；
(5) at a temperature of 50～90 DEG C aging 6～72 hours；
(6) at a temperature of 80～120 DEG C, drying is dried；
(7) roasting 4～12 hours at 350～500 DEG C；
(8) solid particle step (7) obtained is in atmosphere of hydrogen, reduction 3～8 hours at 300～400 DEG C, i.e.
Obtain catalyst of the present invention.
Preparation process as described above, it is characterised in that the nickel described in step (1), copper, the inorganic salt of zinc are preferably
Water miscible metal nitrate or metal chlorination salt.
Preparation process as described above, it is characterised in that the positive esters of silicon acis in silicon source described in step (2), just can be
One or several mixture in methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate；Described solvent alcohol,
Can be one or several mixture in methanol, ethanol, propanol, butanol；Described hydrolytic reagent acid, can be nitric acid, salt
One or several mixture in acid, acetic acid, citric acid.
Preparation process as described above, it is characterised in that in step (1) and step (2), the deionized water of addition, solvent
Alcohol, metal inorganic salt (amount of total material of nickel salt, mantoquita and three kinds of salt of zinc salt), the amount of material of the silicon source each material of positive esters of silicon acis
Than being 40:2～5:0.5～2:1, in metal inorganic salt the amount of the material of nickel salt, mantoquita and three kinds of salt of zinc salt than for 1:0.1～
0.5:0.25～1, addition is deionized water weight 0.5%～the 2% of hydrolytic reagent acid.
Catalyst prepared by preparation method as described above, its specific surface area is 300～500m2/ g, pore volume exists
0.2～0.5g/cm3。
A kind of by the method for Isosorbide-5-Nitrae-butynediols selective hydrogenation synthesis Isosorbide-5-Nitrae-butylene glycol, by catalyst filling in fixing
Bed reaction tube in, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure at 300～400 DEG C activate 6 hours, so
After system response temperature is down to 40～150 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen be continually fed in reactor and react,
The mol ratio controlling Isosorbide-5-Nitrae-butynediols and hydrogen is 1:1.1～1:5, and hydrogen partial pressure is 0.2～2.5Mpa.
The as described above method being synthesized Isosorbide-5-Nitrae-butylene glycol by Isosorbide-5-Nitrae-butynediols selective hydrogenation, reaction temperature is
40～150 DEG C, preferably 50～80 DEG C；The Feed space velocities of 1,4-butynediols is 0.3～2.0h-1, preferably 0.6～1.2h-1；
Isosorbide-5-Nitrae-butynediols is 1:1.1～1:5, preferably 1:1.2～1:2.0 with the mol ratio of hydrogen；Hydrogen partial pressure be 0.2～
2.5Mpa, preferably 0.5～1.5Mpa.
The as described above method being synthesized Isosorbide-5-Nitrae-butylene glycol by Isosorbide-5-Nitrae-butynediols selective hydrogenation, raw material not only may be used
Think sterling Isosorbide-5-Nitrae-butynediols, and the crude product Isosorbide-5-Nitrae-butyne diol solutions that can also prepare for Lei Pafa.This slightly
Product 1,4-butynediols usually contains about 40～other impurity of 60wt% water, 0.1～1wt%.
The present invention provides the catalyst of Isosorbide-5-Nitrae-butynediols selective hydrogenation Isosorbide-5-Nitrae-butylene glycol, its preparation process letter
Single, and avoid precious metal palladium selected in conventional selective hydrocatalyst, therefore the holistic cost of catalyst is relatively low.
The catalyst that the method provided by the present invention is prepared, its specific surface area is up to 300～500m3/ g, activity component metal
Nickel is nanoscale (4～10nm), therefore has higher catalysis activity.
Detailed description of the invention
The invention will be further described for following example, but content not thereby limiting the invention.
In the examples below, Isosorbide-5-Nitrae-butynediols is crude product Isosorbide-5-Nitrae-butynediols, containing 45wt% moisture content.Unclassified stores is equal
Come from commercially available.
Embodiment 1
Solution A: 400g deionized water, 84.94g Nickelous nitrate hexahydrate, 10.8g Gerhardite, 26.06g six is hydrated
Zinc nitrate；Solution B: 115.62g tetraethyl orthosilicate, 102.28g ethanol, 2g acetic acid.After solution A is added dropwise in solution B,
Stirring 12h under room temperature, then stand 24h, then 70 DEG C of aging 24h, after going out still, 100 DEG C are dried, 450 DEG C of roasting 6h.This catalyst
It is labeled as C-A.
C-A is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 2
Solution A: 400g deionized water, 101.20g Nickelous nitrate hexahydrate, 29.43g Gerhardite, 51.76g six water
Close zinc nitrate；Solution B: 115.62g tetraethyl orthosilicate, 76.71g ethanol, 2.5g acetic acid.Solution A is added dropwise in solution B
After, stir 12h under room temperature, then stand 24h, then 70 DEG C of aging 48h, after going out still, 100 DEG C are dried, 500 DEG C of roasting 5h.This catalysis
Agent is labeled as C-B.
C-B is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 3
Solution A: 400g deionized water, 154.34g Nickelous nitrate hexahydrate, 55.14g Gerhardite, 63.16g six water
Close zinc nitrate；Solution B: 115.62g tetraethyl orthosilicate, 115.06g ethanol, 2.5g acetic acid.Solution A is added dropwise to solution B
After in, stirring 12h, then stand 24h, then 70 DEG C of aging 36h under room temperature, after going out still, 100 DEG C are dried, 500 DEG C of roasting 8h.This urges
Agent is labeled as C-C.
C-C is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 4
Solution A: 400g deionized water, 78.98g Nickelous nitrate hexahydrate, 25.70g Gerhardite, 54.94g six is hydrated
Zinc nitrate；Solution B: 115.62g tetraethyl orthosilicate, 127.84g ethanol, 2g acetic acid.After solution A is added dropwise in solution B,
Stirring 12h under room temperature, then stand 24h, then 70 DEG C of aging 48h, after going out still, 100 DEG C are dried, 500 DEG C of roasting 8h.This catalyst
It is labeled as C-D.
C-D is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 5
Solution A: 400g deionized water, 91.33g Nickelous nitrate hexahydrate, 26.56g Gerhardite, 65.40g six is hydrated
Zinc nitrate；Solution B: 115.62g tetraethyl orthosilicate, 102.28g ethanol, 3.0g citric acid.Solution A is added dropwise to solution B
After in, stirring 12h, then stand 24h, then 70 DEG C of aging 48h under room temperature, after going out still, 100 DEG C are dried, 500 DEG C of roasting 8h.This urges
Agent is labeled as C-E.
C-E is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 6
Solution A: 400g deionized water, 101.20g Nickelous nitrate hexahydrate, 29.43g Gerhardite, 51.76g six water
Close zinc nitrate；Solution B: 84.48g methyl silicate, 71.13g methanol, 2g acetic acid.After solution A is added dropwise in solution B,
Stirring 12h under room temperature, then stand 12h, then 60 DEG C of aging 18h, after going out still, 100 DEG C are dried, 500 DEG C of roasting 8h.This catalyst
It is labeled as C-F.
C-F is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 7
Solution A: 400g deionized water, 130.86g Nickelous nitrate hexahydrate, 38.05g Gerhardite, 66.94g six water
Close zinc nitrate；Solution B: 177.90g butyl silicate, 130.86g n-butyl alcohol, 2.5g 37% concentrated hydrochloric acid.Solution A is dropwise added
After entering to solution B, stirring 12h, then stand 24h, then 85 DEG C of aging 48h under room temperature, after going out still, 100 DEG C are dried, 500 DEG C of roastings
Burn 8h.This catalyst is labeled as C-G.
C-G is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 60 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 0.8h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.5Mpa.
Embodiment 8
C-B is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 80 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 1.5h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 0.8Mpa.
Embodiment 9
C-B is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 100 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 1.2h-1, Isosorbide-5-Nitrae-butynediols is 1:2 with the mol ratio of hydrogen, and hydrogen partial pressure is 1.2Mpa.
Embodiment 10
C-B is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 120 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 1.5h-1, Isosorbide-5-Nitrae-butynediols is 1:3 with the mol ratio of hydrogen, and hydrogen partial pressure is 0.5Mpa.
Embodiment 11
C-B is filled in fixed bed reaction pipe, be passed through nitrogen displacement after be passed through again 50ml/min hydrogen under normal pressure
Activate 6h at 300 DEG C, treat that system response temperature is down to 140 DEG C, be passed through Isosorbide-5-Nitrae-butynediols and hydrogen, Isosorbide-5-Nitrae-butynediols air speed
For 1.8h-1, Isosorbide-5-Nitrae-butynediols is 1:4 with the mol ratio of hydrogen, and hydrogen partial pressure is 2.0Mpa.
The specific surface area of table 1 each sample catalyst and pore volume
| Catalyst is numbered | Specific surface area (m2/g) | Pore volume (g/cm3) |
| C-A | 314 | 0.23 |
| C-B | 469 | 0.46 |
| C-C | 427 | 0.31 |
| C-D | 473 | 0.40 |
| C-E | 385 | 0.27 |
| C-F | 466 | 0.43 |
| C-G | 484 | 0.41 |
Table 2 each sample catalyst catalytic performance at different conditions
Visible, the present invention provides the catalyst of Isosorbide-5-Nitrae-butynediols selective hydrogenation Isosorbide-5-Nitrae-butylene glycol, preparation process
Relatively easy, low cost, it is important that catalysis activity is high.
Claims (9)
1. the preparation method of a nickel-base catalyst, it is characterised in that this nickel-base catalyst uses sol-gel process to prepare, specifically
Preparation process is as follows:
(1) nickel, copper, the inorganic salt of zinc are dissolved in deionized water, form solution A；
(2) positive for silicon source esters of silicon acis, solvent alcohol and hydrolytic reagent acid are mixed, form solution B；
(3) after solution A being added dropwise in solution B, and it is stirred at room temperature 1～24 hour；
(4) room temperature stands 6～72 hours；
(5) at a temperature of 50～90 DEG C aging 6～72 hours；
(6) at a temperature of 80～120 DEG C, drying is dried；
(7) roasting 4～12 hours at 350～500 DEG C；
(8) solid particle step (7) obtained is in atmosphere of hydrogen, reduces 3～8 hours, i.e. obtain at 300～400 DEG C
Catalyst of the present invention.
Preparation method the most according to claim 1, it is characterised in that the nickel described in step (1), copper, the inorganic salt of zinc are
Water miscible metal nitrate or metal chlorination salt.
Preparation method the most according to claim 1, it is characterised in that the positive esters of silicon acis in silicon source described in step (2), is selected from
One or several mixture in methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate；Described solvent
Alcohol, one or several mixture in methanol, ethanol, propanol, butanol；Described hydrolytic reagent acid, selected from nitric acid, salt
One or several mixture in acid, acetic acid, citric acid.
Preparation method the most according to claim 1, it is characterised in that in step (1) and step (2), the deionization of addition
Water, solvent alcohol, metal inorganic salt, the positive esters of silicon acis in silicon source the amount of material than for 40:2～5:0.5～2:1；Described metal inorganic
In salt, the amount of the material of nickel salt, mantoquita and three kinds of salt of zinc salt is than for 1:0.1～0.5:0.25～1；The addition of described hydrolytic reagent acid
Amount is the 0.5%～2% of deionized water weight.
5. the catalyst that the preparation method as described in Claims 1 to 4 any one obtains, its specific surface area is 300～500m2/
G, pore volume is 0.2～0.5g/cm3。
6. catalyst synthesizes answering during 1,4-butylene glycol reacts in 1,4-butynediols selective hydrogenation as claimed in claim 5
With.
Application the most according to claim 6, it is characterised in that: by described catalyst filling in fixed bed reaction pipe, logical
It is passed through 50ml/min hydrogen again after entering nitrogen displacement to activate 6 hours at 300～400 DEG C under normal pressure, then by system response
Temperature is down to 40～150 DEG C, is passed through Isosorbide-5-Nitrae-butynediols and hydrogen is continually fed in reactor and reacts, and controls Isosorbide-5-Nitrae-butine
Glycol is 1:1.1～1:5 with the mol ratio of hydrogen, and hydrogen partial pressure is 0.2～2.5Mpa.
Application the most according to claim 7, it is characterised in that: reaction temperature is 40～150 DEG C；Entering of 1,4-butynediols
Material air speed is 0.3～2.0h-1；1,4-butynediols is 1:1.1～1:5 with the mol ratio of hydrogen；Hydrogen partial pressure be 0.2～
2.5Mpa。
9. according to the application described in claim 6～8 any one, it is characterised in that: raw material Isosorbide-5-Nitrae-butynediols is by thunder handkerchief
The thick 1,4-butynediols aqueous solution that synthesis obtains.
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| CN107185541A (en) * | 2017-06-13 | 2017-09-22 | 中触媒新材料股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN108097254A (en) * | 2017-12-25 | 2018-06-01 | 新疆大学 | Nickel-base catalyst for 1,4- butynediols hydrogenation synthesis 1,4- butanediols and preparation method thereof |
| CN109647531A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of hydrogenation technique of catalyst for adding hydrogen for 1,4- butynediols and preparation method thereof and 1,4- butynediols |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185541A (en) * | 2017-06-13 | 2017-09-22 | 中触媒新材料股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN109647531A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of hydrogenation technique of catalyst for adding hydrogen for 1,4- butynediols and preparation method thereof and 1,4- butynediols |
| CN109647531B (en) * | 2017-10-10 | 2022-02-08 | 中国石油化工股份有限公司 | Catalyst for hydrogenation of 1, 4-butynediol, preparation method thereof and hydrogenation process of 1, 4-butynediol |
| CN108097254A (en) * | 2017-12-25 | 2018-06-01 | 新疆大学 | Nickel-base catalyst for 1,4- butynediols hydrogenation synthesis 1,4- butanediols and preparation method thereof |
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