CN107952444A - A kind of method of catalyst with liquid-phase hydrogenatin and preparation method thereof and preparing furancarbinol from liquid-phase furol hydrogenation - Google Patents
A kind of method of catalyst with liquid-phase hydrogenatin and preparation method thereof and preparing furancarbinol from liquid-phase furol hydrogenation Download PDFInfo
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- CN107952444A CN107952444A CN201610900694.3A CN201610900694A CN107952444A CN 107952444 A CN107952444 A CN 107952444A CN 201610900694 A CN201610900694 A CN 201610900694A CN 107952444 A CN107952444 A CN 107952444A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007791 liquid phase Substances 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical compound OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 16
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 15
- 229960004643 cupric oxide Drugs 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- -1 metals Hydroxide Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 78
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910019580 Cr Zr Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 19
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 238000004438 BET method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940078480 calcium levulinate Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical class [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to catalyst field, the method for disclosing a kind of catalyst with liquid-phase hydrogenatin and preparation method thereof and preparing furancarbinol from liquid-phase furol hydrogenation.The catalyst contains copper component, chromium component and auxiliary agent, wherein, the auxiliary agent is provided by the compound of at least one metallic element containing group ivb；With elemental metal, the molar ratio of the copper component and group ivb metal component is 5 20：1.The catalyst with liquid-phase hydrogenatin provided by the invention containing Cu Cr Zr is used in the reaction process of preparing furancarbinol from liquid-phase furol hydrogenation, which has higher catalytic activity and furfuryl alcohol selectivity.
Description
Technical field
The present invention relates to furfuryl alcohol production field, and in particular, to and it is a kind of that there is the catalyst of liquid-phase hydrogenatin, there is liquid
The preparation method of the catalyst of phase hydrogenating function, and catalyst obtained by this method, and preparing furancarbinol from liquid-phase furol hydrogenation
Method.
Background technology
Furfuryl alcohol is a kind of important industrial chemicals, and second phthalein propionic acid can be made through hydrolysis in furfuryl alcohol, be nutrient drug calcium levulinate
Intermediate；Furan type resin, furfuryl alcohol-Lauxite and phenolic resin of better performances etc. can be produced using furfuryl alcohol as raw material；Chaff
Alcohol is the good solvent and rocket fuel of furane resins, varnish, pigment again；In addition, furfuryl alcohol synthetic fibers, rubber, pesticide and
Also it is widely used in foundary industry.
The production technology of furfuryl alcohol can be divided into two kinds of liquid-phase hydrogenatin technique and gas phase hydrogenation technique at present.China is production furfuryl alcohol
Big country, mainly to be based on preparing furancarbinol from liquid-phase furol hydrogenation.It is that the catalyst with liquid-phase hydrogenatin is broadly divided into copper chromium
System and two class of copper silicon systems, the two is compared, the former activity and selectivity is preferable, and separation is easier to, but higher price, causes two kinds
The total usage amount of catalyst in production remains basically stable.
CN1404922A discloses addition metallic nickel Cu-Cr catalyst, is prepared using coprecipitation, is in reaction temperature
180-200 DEG C, under reaction pressure 3.5-5.0MPa hydroconversion conditions, furfural conversion ratio is more than 99.2%, and furfuryl alcohol is selectively more than
96%.CN1398670A and CN1562477A individually discloses the VIIIth race's precious metals pt of addition and the Cu-Cr catalyst of Pd, catalysis
Agent preparation method is coprecipitation, expensive although both catalyst activities are preferable.
Coprecipitation prepares catalyst and generally comprises with liquid, neutralization, washing, filtering, drying, roasting, and process is more and is not easy
Control, reappearance is poor, waste water, the exhaust gas of a large amount of pollution environment can be also produced in preparation process in addition, in environmental protection cry
The today grown to even greater heights, it is imperative to develop environmentally protective method for preparing catalyst.
Therefore, it is badly in need of finding that a kind of preparation method is simple at present, and it is new with higher catalytic activity and selectivity
Type has the function of the catalyst of liquid-phase hydrogenatin.
The content of the invention
The purpose of the invention is to overcome it is existing there is drawbacks described above existing for the catalyst of liquid-phase hydrogenatin, carry
A kind of preparation method that there is the catalyst of liquid-phase hydrogenatin, there is the catalyst of liquid-phase hydrogenatin has been supplied, and by this
Catalyst made from method, and the method for preparing furancarbinol from liquid-phase furol hydrogenation.Catalyst provided by the invention is used for furfural liquid phase
The process of Hydrogenation furfuryl alcohol, catalytic activity and selectivity significantly improve.
To achieve these goals, should in a first aspect, there is the catalyst of liquid-phase hydrogenatin the present invention provides a kind of
Catalyst contains copper component, chromium component and auxiliary agent, wherein, the auxiliary agent by least one metallic element containing group ivb chemical combination
Thing provides；With elemental metal, the molar ratio of the copper component and auxiliary agent is 5-20：1.
Second aspect, present invention also offers a kind of preparation method with the catalyst of liquid-phase hydrogenatin, this method
Including：The precursor of cupric oxide, chrome green and auxiliary agent is ground, then is dried and roasts successively；Wherein, it is described to help
The precursor of agent is the hydroxide and/or oxide of group ivb metal, is preferably the hydroxide of Section IV B group metals, more preferably
For zirconium hydroxide and/or titanium hydroxide, more preferably zirconium hydroxide；With elemental metal, the cupric oxide and auxiliary agent
The molar ratio of the dosage of precursor is 5-20：1.
The third aspect, present invention also offers what is be prepared by the above method to have the function of the catalyst of liquid-phase hydrogenatin.
Fourth aspect, present invention also offers a kind of method of preparing furancarbinol from liquid-phase furol hydrogenation, wherein, this method includes：
Under conditions of preparing furancarbinol from liquid-phase furol hydrogenation reaction, above-mentioned catalyst is contacted with furfural.
The present inventor has found in the course of the research, and catalyst, one side reactant solid are prepared using ball-milling method
Crush under external force, particle subtracts so that surface area increases sharply and forms fine particle, while different plant species are able to dividing
Reach on sub- scale and come into full contact with；Another aspect reactant and product particles occur under the static(al) shearing force collective effect of reaction
Deformation, so as to produce a large amount of lattice defects, is conducive to strengthen the phase in catalyst between the precursor of cupric oxide, chromium oxide and auxiliary agent
Interaction and the activity for improving catalyst.Although traditional liquid-phase coprecipitation can also realize different component on molecular scale
Mixing, but due to external force act on very little and be difficult to produce larger lattice defect, additionally there may be precipitation by metallic ion
Not exclusively or because precursor constituent is uneven caused by settling velocity is different and particle hard aggregation caused by compare surface
The shortcomings of product declines.
In addition, auxiliary agent provided by the invention has the function that structural promoter, after introducing auxiliary agent in the catalyst, copper is promoted
The surface enrichment of ion；Meanwhile auxiliary agent provided by the invention is also equipped with electronic auxiliary and acts on, the metal ion in auxiliary agent dissolves in copper
Base catalyst crystal lattice, changes the coordination environment of Cu in catalyst, stablizes chain carrier, therefore can be in furfural liquid phase
Excellent catalytic activity is shown in the reaction of Hydrogenation furfuryl alcohol.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, there is the catalyst of liquid-phase hydrogenatin the present invention provides a kind of, the catalyst contain copper component,
Chromium component and auxiliary agent, wherein, the auxiliary agent is provided by the compound of at least one metallic element containing group ivb；With metallic element
The molar ratio of meter, the copper component and auxiliary agent is 5-20：1, it is preferably 5-13：1.
According to the present invention, with elemental metal, the molar ratio of the copper component and the chromium component can be 0.9-2.75：
1, it is preferably 0.9-1.15：1.
According to the present invention, there is no particular limitation for form of the present invention to the copper component, as long as containing copper,
For example, the copper component can exist in the form of the oxide of copper, it is preferably cupric oxide.
According to the present invention, there is no particular limitation for form of the present invention to the chromium component, as long as containing chromium,
For example, the chromium component can exist in the form of the oxide of chromium, it is preferably zirconium sesquioxide.
According to the present invention, there is no particular limitation for form of the present invention to the auxiliary agent, for example, can be with group ivb gold
The form of the oxide of category exists, and is preferably zirconium oxide and/or titanium oxide, more preferably zirconium oxide.
According to the present invention, the particle diameter of the catalyst can be less than or equal to 800 mesh；Specific surface area is 10-150m2/ g, it is excellent
Elect 35-125m as2/g；Pore volume is 0.1-0.6mL/g, is preferably 0.18-0.46mL/g.
Second aspect, present invention also offers a kind of method for the catalyst for preparing and having the function of liquid-phase hydrogenatin, this method
Including：The precursor of cupric oxide, chrome green and auxiliary agent is ground, then is dried and roasts successively；
Wherein, the precursor of the auxiliary agent is the hydroxide and/or oxide of group ivb metal, is preferably Section IV B groups gold
The hydroxide of category, more preferably zirconium hydroxide and/or titanium hydroxide, more preferably zirconium hydroxide；With elemental metal,
The molar ratio of the dosage of the precursor of the cupric oxide and auxiliary agent is 5-20：1, it is preferably 5-13：1.
According to the present invention, with elemental metal, the molar ratio of the cupric oxide and the dosage of the chrome green can be with
For 0.9-2.75：1, it is preferably 0.9-1.15：1.
According to the present invention, the particle diameter of the cupric oxide can be less than or equal to 100 mesh；The particle diameter of the chromium oxide can be less than
Equal to 100 mesh；The particle diameter of the precursor of the auxiliary agent can be less than or equal to 100 mesh.
In the present invention, the addition sequence of the precursor of the cupric oxide, chrome green and auxiliary agent is not limited particularly
It is fixed, it can be ground with random order.
According to the present invention, the mode of the grinding can be ball milling.
According to the present invention, the condition of the ball milling can include：Ratio of grinding media to material is 5-30：1, rotating speed is 300-1500 revs/min
Clock, when the time is 12-72 small.
According to the present invention, the condition of the drying can include：Drying temperature is 100-120 DEG C, drying time 10-20
Hour.
According to the present invention, the condition of the roasting can include：Calcination temperature is 300-400 DEG C, and roasting time is small for 2-6
When.
The third aspect, present invention also offers what is be prepared by the above method to have the function of the catalyst of liquid-phase hydrogenatin.
According to the present invention, the particle diameter of the catalyst can be less than or equal to 800 mesh；Specific surface area is 10-150m2/ g, it is excellent
Elect 35-125m as2/g；Pore volume is 0.1-0.6mL/g, is preferably 0.18-0.46mL/g.
Fourth aspect, present invention also offers a kind of method of preparing furancarbinol from liquid-phase furol hydrogenation, this method includes：In furfural
Under conditions of the reaction of liquid-phase hydrogenatin furfuryl alcohol, above-mentioned catalyst is contacted with furfural.
According to the present invention, the condition of the reaction can include：Reaction temperature is 180-200 DEG C, reaction pressure 5-
8MPa.Relative to 100mL furfurals, the dosage of the catalyst is preferably 1-2g.
In the present invention, the method for the preparing furancarbinol from liquid-phase furol hydrogenation further includes：Contact the depositing in co-catalyst
In lower progress.Wherein, the co-catalyst can be the conventional selection of this area, for example, can be calcium oxide.
The present invention will be described in detail by way of examples below.
In following embodiments, furfural conversion ratio=(molal quantity of furfural in molal quantity-product of furfural in reactant)/anti-
Answer molal quantity × 100% of furfural in thing；
The molal quantity of furfuryl alcohol in furfuryl alcohol selectivity=product/(in reactant in molal quantity-product of furfural furfural mole
Number) × 100%.
Embodiment 1
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh the Cr that 30g particle diameters are less than or equal to 100 mesh less than or equal to CuO powder, the 26.1g particle diameters of 100 mesh2O3Powder and
5.5g particle diameters are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in ball grinder, is 700 revs/min in rotating speed, ratio of grinding media to material is
15：Under 1 ball milling condition, when ball milling 24 is small, take out mixture, at 120 DEG C it is dry 12 it is small when, then in Muffle furnace in
When 350 DEG C of roastings 4 are small, catalyst is obtained.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 1.1：1, Cu/Zr molar ratio is 11：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 700 mesh；Detected through BET method, specific surface area is
83m2/ g, pore volume 0.35mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 100%, furfuryl alcohol selectivity 99.32%.
Embodiment 2
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh the Cr that 30g particle diameters are less than or equal to 100 mesh less than or equal to CuO powder, the 26.1g particle diameters of 100 mesh2O3Powder and
5.5g particle diameters are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in ball grinder, is 300 revs/min in rotating speed, ratio of grinding media to material 5：
Under 1 ball milling condition, when ball milling 12 is small, mixture is taken out, when drying 12 is small at 120 DEG C, then in 350 DEG C in Muffle furnace
Roast 4 it is small when, obtain catalyst.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 1.1：1, Cu/Zr molar ratio is 11：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 400 mesh；Detected through BET method, specific surface area is
35m2/ g, pore volume 0.18mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure is 0.45h under conditions of 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural conversion
Rate is 98%, furfuryl alcohol selectivity 97.3%.
Embodiment 3
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh the Cr that 30g particle diameters are less than or equal to 100 mesh less than or equal to CuO powder, the 26.1g particle diameters of 100 mesh2O3Powder and
5.5g particle diameters are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in ball grinder, is 1500 revs/min in rotating speed, ratio of grinding media to material is
30：Under 1 ball milling condition, when ball milling 72 is small, take out mixture, at 120 DEG C it is dry 12 it is small when, then in Muffle furnace in
When 350 DEG C of roastings 4 are small, catalyst is obtained.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 1.1：1, Cu/Zr molar ratio is 11：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 800 mesh；BET method detects, specific surface area 125m2/
G, pore volume 0.46mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 100%, furfuryl alcohol selectivity 99.1%.
Embodiment 4
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh the Cr that 30g particle diameters are less than or equal to 100 mesh less than or equal to CuO powder, the 31g particle diameters of 100 mesh2O3Powder and
10.9g particle diameters are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in ball grinder, is 700 revs/min in rotating speed, ratio of grinding media to material is
15：Under 1 ball milling condition, when ball milling 24 is small, take out mixture, at 120 DEG C it is dry 12 it is small when, then in Muffle furnace in
When 350 DEG C of roastings 4 are small, catalyst is obtained.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 0.92：1, Cu/Zr molar ratio is 5.5：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 700 mesh；Detected through BET method, specific surface area is
86m2/ g, pore volume 0.36mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 97.3%, furfuryl alcohol selectivity 98.5%.
Embodiment 5
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh the Cr that 30g particle diameters are less than or equal to 100 mesh less than or equal to CuO powder, the 24.9g particle diameters of 100 mesh2O3Powder and
4.6g particle diameters are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in ball grinder, is 700 revs/min in rotating speed, ratio of grinding media to material is
15：Under 1 ball milling condition, when ball milling 24 is small, take out mixture, at 120 DEG C it is dry 12 it is small when, then in Muffle furnace in
When 350 DEG C of roastings 4 are small, catalyst is obtained.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 1.15：1, Cu/Zr molar ratio is 13：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 700 mesh；Detected through BET method, specific surface area is
78m2/ g, pore volume 0.33mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 99.7%, furfuryl alcohol selectivity 97.36%.
Embodiment 6
The present embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares catalyst, unlike, use Ti (OH)4Instead of Zr (OH)4。
Screened analysis method detection, the particle diameter of the catalyst is less than or equal to 700 mesh；Detected through BET method, specific surface area is
81m2/ g, pore volume 0.38mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 98.2%, furfuryl alcohol selectivity 95.3%.
Embodiment 7
Weigh the Cr that 30g granularities are less than or equal to the CuO powder of 100 mesh, 26.1g granularities are less than or equal to 100 mesh2O3Powder and
5.5g granularities are less than or equal to the Zr (OH) of 100 mesh4Powder, is positioned in there-necked flask, and above-mentioned material is made under strength mechanical agitation
It is sufficiently mixed, takes out mixture, when 120 DEG C of dryings 12 are small, is then catalyzed in Muffle furnace when 350 DEG C of roastings 4 are small
Agent.
In the catalyst, it can be calculated according to the inventory of raw material, with elemental metal, the molar ratio of Cu/Cr
It is 1.1：1, Cu/Zr molar ratio is 11：1.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 100 mesh；Detected through BET method, specific surface area is
22m2/ g, pore volume 0.13mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 89.26%, and furfuryl alcohol is selectively 78.32%.
Comparative example 1
Method according to embodiment 1 prepares catalyst, unlike, Zr (OH) is not added4Powder, obtains catalyst.
Screened analysis method detection, the particle diameter of the catalyst are less than or equal to 800 mesh；Detected through BET method, specific surface area is
82m2/ g, pore volume 0.36mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 98.5%, and furfuryl alcohol is selectively 90.3%.
Comparative example 2
Method according to embodiment 1 prepares catalyst, unlike, use Nb (OH)5Instead of Zr (OH)4。
Screened analysis method detection, the particle diameter of the catalyst is less than or equal to 700 mesh；Detected through BET method, specific surface area is
91m2/ g, pore volume 0.41mL/g.
Catalyst 3.5g and 300mL furfurals are added in autoclave at the same time, add CaO 0.4g.It is in reaction temperature
200 DEG C, pressure reacts 0.45h under conditions of being 7.5MPa, and reaction product is analyzed using gas-chromatography, is computed furfural
Conversion ratio is 91%, furfuryl alcohol selectivity 88.5%.
It was found from the result of above example compares, there is liquid-phase hydrogenatin containing Cu-Cr-Zr by provided by the invention
The catalyst of function is used in the reaction process of preparing furancarbinol from liquid-phase furol hydrogenation, which has higher catalytic activity and chaff
Alcohol selectivity.In addition, comparing embodiment 1 and comparative example 1-2 can be seen that comparative example 1 due to being not introduced into of the present invention help
Agent, under the reaction condition identical with use of the present invention, furfuryl alcohol selectivity is obvious to be reduced, and comparative example 2 uses another metal
Component, furfural conversion ratio and furfuryl alcohol are selectively significantly lower than embodiment 1.Especially, from embodiment 1-3 and the result of embodiment 7
As can be seen that the method using the present invention including ball milling step can obtain the catalytic activity for further improving catalyst.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of have the function of the catalyst of liquid-phase hydrogenatin, it is characterised in that the catalyst contains copper component, chromium component and helps
Agent, wherein, the auxiliary agent is provided by the compound of at least one metallic element containing group ivb；With elemental metal, the copper group
It is 5-20 to divide with the molar ratio of group ivb metal component：1, it is preferably 5-13：1.
2. catalyst according to claim 1, wherein, with elemental metal, the copper component is rubbed with the chromium component
Your ratio is 0.9-2.75：1, it is preferably 0.9-1.15：1.
3. catalyst according to claim 1 or 2, wherein, the copper component exists in the form of the oxide of copper, preferably
For cupric oxide；The chromium component exists in the form of chromated oxide, is preferably chrome green；The auxiliary agent is with group ivb gold
The form of the oxide of category exists, and is preferably zirconium oxide and/or titanium oxide, more preferably zirconium oxide.
4. according to the catalyst described in any one in claim 1-3, wherein, the particle diameter of the catalyst is less than or equal to 800
Mesh；Specific surface area is 10-150m2/ g, is preferably 35-125m2/g；Pore volume is 0.1-0.6mL/g, is preferably 0.18-
0.46mL/g。
A kind of 5. method for preparing the catalyst with liquid-phase hydrogenatin, it is characterised in that this method includes：By cupric oxide,
The precursor of chrome green and auxiliary agent is ground, then is dried and is roasted successively；
Wherein, the precursor of the auxiliary agent is the hydroxide and/or oxide of group ivb metal, is preferably Section IV B group metals
Hydroxide, more preferably zirconium hydroxide and/or titanium hydroxide, more preferably zirconium hydroxide；It is described with elemental metal
The molar ratio of the dosage of the precursor of cupric oxide and auxiliary agent is 5-20：1, it is preferably 5-13：1.
6. according to the method described in claim 5, wherein, with elemental metal, the cupric oxide and the chrome green
The molar ratio of dosage is 0.9-2.75：1, it is preferably 0.9-1.15：1.
7. the method according to claim 5 or 6, wherein, the particle diameter of the cupric oxide is less than or equal to 100 mesh；The oxidation
The particle diameter of chromium is less than or equal to 100 mesh；The particle diameter of the precursor of the auxiliary agent is less than or equal to 100 mesh.
8. according to the method described in claim 5, wherein, the mode of the grinding is ball milling.
9. according to the method described in claim 8, wherein, the condition of the ball milling includes：Ratio of grinding media to material is 5-30：1, rotating speed is
300-1500 revs/min, when the time is 12-72 small.
10. according to the method described in any one in claim 5-9, wherein, the condition of the drying includes：Drying temperature is
100-120 DEG C, when drying time is 10-20 small.
11. according to the method described in any one in claim 5-10, wherein, the condition of the roasting includes：Calcination temperature
For 300-400 DEG C, when roasting time is 2-6 small.
12. there is the catalyst of liquid-phase hydrogenatin as what the method described in any one in claim 5-11 was prepared.
13. catalyst according to claim 12, wherein, the particle diameter of the catalyst is less than or equal to 800 mesh；Specific surface area
For 10-150m2/ g, is preferably 35-125m2/g；Pore volume is 0.1-0.6mL/g, is preferably 0.18-0.46mL/g.
A kind of 14. method of preparing furancarbinol from liquid-phase furol hydrogenation, it is characterised in that this method includes：In furfural liquid-phase hydrogenatin chaff
Under conditions of alcohol reaction, the catalyst described in any one in claim 1-4,12 and 13 is contacted with furfural.
15. according to the method for claim 14, wherein, the condition of the reaction includes：Reaction temperature is 180-200 DEG C,
Reaction pressure is 5-8MPa；Relative to 100mL furfurals, the dosage of the catalyst is 1-2g.
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| CN110871085A (en) * | 2018-08-30 | 2020-03-10 | 淄博张店东方化学股份有限公司 | Supported catalyst for preparing furfuryl alcohol by catalytic hydrogenation of furfural and preparation method and application thereof |
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| CN110871085B (en) * | 2018-08-30 | 2022-11-29 | 淄博张店东方化学股份有限公司 | Supported catalyst for preparing furfuryl alcohol by catalytic hydrogenation of furfural and preparation method and application thereof |
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