CN108906096A - A kind of ordered mesopore carbon for alcohol dehydrogenase encapsulates metal-carbide catalyst and preparation - Google Patents
A kind of ordered mesopore carbon for alcohol dehydrogenase encapsulates metal-carbide catalyst and preparation Download PDFInfo
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- CN108906096A CN108906096A CN201810811544.4A CN201810811544A CN108906096A CN 108906096 A CN108906096 A CN 108906096A CN 201810811544 A CN201810811544 A CN 201810811544A CN 108906096 A CN108906096 A CN 108906096A
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- metal
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- ordered mesopore
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- carbide catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 102000007698 Alcohol dehydrogenase Human genes 0.000 title claims abstract description 12
- 108010021809 Alcohol dehydrogenase Proteins 0.000 title claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 11
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 11
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 11
- 229940033123 tannic acid Drugs 0.000 claims abstract description 11
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 11
- 229920002258 tannic acid Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 238000005538 encapsulation Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000007357 dehydrogenase reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 7
- 229910039444 MoC Inorganic materials 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ordered mesopore carbons for alcohol dehydrogenase to encapsulate metal-carbide catalyst and preparation, belongs to Industrial Catalysis and fine field of chemical technology.The present invention independently fills template, tannic acid and source metal blending ball milling, and then high temperature cabonization is made ordered mesopore carbon and encapsulates metal-carbide catalyst.The catalyst prepares aldehyde for the alcohol dehydrogenase reaction of anaerobic agent, obtains excellent catalytic activity and selectivity, and catalyst simply can be recycled and be reused.The advantages of this hair, is, method for preparing catalyst simplicity is easily operated, solvent-free, speed is fast, can be mass, more importantly the unique order mesoporous confinement structure of catalyst can not only effectively accelerate the mass transfer of reaction substrate, the solution-off and reunion of active constituent can be also prevented, to impart its excellent catalytic performance.
Description
Technical field
The present invention relates to a kind of ordered mesopore carbons for alcohol dehydrogenase to encapsulate metal-carbide catalyst and preparation, using template
Self assembly is blended in agent, tannic acid and source metal ball milling, and then high temperature cabonization is prepared ordered mesopore carbon encapsulation metal-carbide and urges
Agent belongs to Industrial Catalysis and fine field of chemical technology.
Background technique
Aldehyde is a kind of important chemical intermediate, is widely used in Minute Organic Synthesis and organic chemical industry's process.Currently, often
The synthetic method for the aldehyde seen is with hydrogen peroxide (H2O2) or oxygen (O2) it is oxidant, under conditions of noble metal is catalyst
Oxidation alcohol obtains.In order to further save cost, energy consumption is reduced, in recent years, people have invested sight more with transition gold
Belonging to (such as Mo, V, Ni, Cu, Co, Mn, Fe and Ti etc.) is catalyst, the alcohol direct dehydrogenation catalytic process of anaerobic agent.
For metal-carbide since its is cheap, stability is good, and has good electronic conduction ability, it is considered to be most has
Desired multiphase non-precious metal catalyst.Although metal-carbide is in electrolysis aquatic products hydrogen, in numerous reactions such as organic matter dehydrogenation
Show excellent catalytic performance, the application in the fine chemicals of synthesis high added value is also relatively fewer, is badly in need of expanding
Application of the metal-carbide in Minute Organic Synthesis field.On the other hand, the catalytic activity of metal-carbide largely depends on
In its structure composition, pattern and crystal structure.Constructing, there is the metal-carbide catalyst of nano pore structure to be conducive to accelerate instead
It answers the mass transfer of substrate and sufficiently exposes active site, to improve catalytic activity.However, traditional preparation method is difficult to point
The uniform good metal-carbide catalyst of lattice structure is dissipated, therefore, designing and develop a kind of simply and effectively construct has
The preparation method of the metal-carbide catalyst of ordered meso-porous structure has important industrial application value.To solve the above-mentioned problems,
Self assembly is blended in template, tannic acid and source metal ball milling by the present invention, and then high temperature cabonization prepares ordered mesopore carbon encapsulation carbon
Change metallic catalyst, and be applied to alcohol dehydrogenase reaction, which has not been reported yet.
Summary of the invention
The present invention be directed to deficiency existing for tradition carbonization metal fabrication methods, a kind of simple process, easy to operate is provided
Ordered mesopore carbon encapsulation metal-carbide catalyst preparation method, and by catalyst be applied to anaerobic agent alcohol dehydrogenase reaction,
Achieve good catalytic effect.
Technical solution of the present invention：A kind of mechanical ball of the ordered mesopore carbon encapsulation metal-carbide catalyst for alcohol dehydrogenase
Grind Preparation Method, it is characterised in that including following procedure：
It according to mass ratio is 1 by template and tannic acid:0.6~1:2 are added in the filling of 30mL stainless steel ball-milling, add simultaneously
Enter the stainless steel ball that 2~6 diameters are 1.2cm, ball milling filling is placed in 10~60min of ball milling on three-dimensional concussion ball milling instrument, concussion
Frequency is 20~40Hz, then addition source metal continuation 30~60min of ball milling, and the mass ratio of source metal and tannic acid is 1:5~
1:2, obtained ball-milled mixtures are placed in tube furnace in 700~900 DEG C of nitrogen atmospheres 2~4h of calcining, heating rate is 2~
10 DEG C/min, obtain ordered mesopore carbon encapsulation metal-carbide catalyst；
The application of above-mentioned ordered mesopore carbon encapsulation metal-carbide catalyst alcohol dehydrogenase reaction, it is characterised in that：By alcohol
With organic solvent according to mass ratio 1:3~1:10 mixing add the ordered mesopore carbon that quality is alcohol quality 1%~8% and encapsulate
Metal-carbide catalyst is 70~120 DEG C in reaction temperature, is stirred to react 4~10h, obtains the mixture containing aldehyde product；
The preparation method of above-mentioned ordered mesopore carbon encapsulation metal-carbide catalyst, which is characterized in that template be P123 or
F127, source metal are one of ammonium molybdate, ammonium tungstate, ammonium metavanadate, molybdenum pentachloride, tungsten chloride, vanadium chloride.
Above-mentioned application, which is characterized in that alcohol is benzyl alcohol, benzyl carbinol, cyclohexanol, benzohydrol, n-butanol, just pungent
One of alcohol, organic solvent are one of acetonitrile, DMF, toluene, DMSO.
Compared with prior art, it is an advantage of the invention that：Catalyst preparation process is simple, is not necessarily to solvent, speed fastly, gained
Metal-carbide catalyst has good crystal structure and ordered mesopore structure, reacts for alcohol dehydrogenase, without oxidant, catalysis
Activity and selectivity is high and catalyst can be recycled and be reused with simple filtration.
Detailed description of the invention
Fig. 1 ordered mesopore carbon encapsulation molybdenum carbide catalyst x-ray diffraction pattern (XRD) prepared by the present invention.
Fig. 2 ordered mesopore carbon prepared by the present invention encapsulates molybdenum carbide catalyst N2Absorption and graph of pore diameter distribution.
Specific embodiment
The present invention is further illustrated below by specific embodiment, but does not limit the present invention.
【Embodiment 1】
It according to mass ratio is 0.8 by F127 and tannic acid:1 is added in the filling of 30mL stainless steel ball-milling, while being added 3 directly
Diameter is the stainless steel ball of 1.2cm, ball milling filling is placed in ball milling 30min, oscillation frequency 30Hz on three-dimensional concussion ball milling instrument, then
The mass ratio of addition ammonium molybdate continuation ball milling 30min, ammonium molybdate and tannic acid is 1:3, obtained ball-milled mixtures are placed in pipe
2h is calcined in formula furnace in 800 DEG C of nitrogen atmospheres, heating rate is 5 DEG C/min, obtains ordered mesopore carbon encapsulation molybdenum carbide catalyst.
Fig. 1 is the XRD diagram that ordered mesopore carbon encapsulates molybdenum carbide catalyst.
Fig. 2 is the N that ordered mesopore carbon encapsulates molybdenum carbide catalyst2Absorption and graph of pore diameter distribution.
【Embodiment 2】
It according to mass ratio is 0.8 by F127 and tannic acid:1 is added in the filling of 30mL stainless steel ball-milling, while being added 3 directly
Diameter is the stainless steel ball of 1.2cm, ball milling filling is placed in ball milling 30min, oscillation frequency 30Hz on three-dimensional concussion ball milling instrument, then
The mass ratio of addition ammonium tungstate continuation ball milling 30min, ammonium molybdate and tannic acid is 1:3, obtained ball-milled mixtures are placed in pipe
3h is calcined in formula furnace in 900 DEG C of nitrogen atmospheres, heating rate is 5 DEG C/min, obtains ordered mesopore carbon encapsulation tungsten carbide catalyst.
【Embodiment 3】
By benzyl alcohol and DMSO according to mass ratio 1:5 mixing add the ordered mesopore carbon that quality is alcohol quality 5% and encapsulate
Molybdenum carbide catalyst is 100 DEG C in reaction temperature, is stirred to react 4h, obtains the mixture containing benzaldehyde product, through gas phase color
The conversion ratio and selectivity of spectrum detection reaction are respectively 98% and 100%.
【Embodiment 4】
By cyclohexanol and DMSO according to mass ratio 1:5 mixing add the ordered mesopore carbon that quality is alcohol quality 5% and encapsulate
Molybdenum carbide catalyst is 100 DEG C in reaction temperature, is stirred to react 6h, obtains the mixture containing cyclohexanone products, through gas phase color
The conversion ratio and selectivity of spectrum detection reaction are respectively 96% and 100%.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (6)
1. a kind of mechanical ball mill preparation method of the ordered mesopore carbon encapsulation metal-carbide catalyst for alcohol dehydrogenase, feature exist
In including following procedure：
It according to mass ratio is 1 by template and tannic acid:0.6~1:2 are added in the filling of 10~100mL stainless steel ball-milling, simultaneously
The stainless steel ball that 2~6 diameters are 1.0~2.0cm is added, by ball milling filling be placed in ball milling 10 on three-dimensional concussion ball milling instrument~
60min, oscillation frequency are 20~40Hz, and source metal is then added and continues 30~60min of ball milling, the quality of source metal and tannic acid
Than being 1:5~1:2, obtained ball-milled mixtures are placed in tube furnace 2~4h of calcining in 700~900 DEG C of nitrogen atmospheres, heating
Rate is 2~10 DEG C/min, obtains ordered mesopore carbon encapsulation metal-carbide catalyst.
2. preparation method according to claim 1, which is characterized in that template is P123 or F127.
3. preparation method according to claim 1, which is characterized in that source metal be ammonium molybdate, ammonium tungstate, ammonium metavanadate,
One of molybdenum pentachloride, tungsten chloride, vanadium chloride.
4. being answered by what the ordered mesopore carbon encapsulation metal-carbide catalyst alcohol dehydrogenase of claim 1 the method preparation reacted
With, it is characterised in that：By pure and mild organic solvent according to mass ratio 1:3~1:10 mixing, add quality be alcohol quality 1%~
8% ordered mesopore carbon encapsulates metal-carbide catalyst, is 70~120 DEG C in reaction temperature, is stirred to react 4~10h, is contained
There is the mixture of aldehyde product.
5. application according to claim 4, which is characterized in that alcohol be benzyl alcohol, benzyl carbinol, cyclohexanol, benzohydrol,
One of n-butanol, n-octyl alcohol.
6. application according to claim 4, which is characterized in that organic solvent is acetonitrile, DMF, toluene, one in DMSO
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810811544.4A CN108906096B (en) | 2018-07-23 | 2018-07-23 | Ordered mesoporous carbon packaged metal carbide catalyst for alcohol dehydrogenation and preparation |
Applications Claiming Priority (1)
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| CN113995837A (en) * | 2021-11-05 | 2022-02-01 | 中国科学院长春应用化学研究所 | Template-free hollow tannic acid-iron nano coordination sphere and preparation method and application thereof |
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| CN111545239A (en) * | 2020-05-29 | 2020-08-18 | 江南大学 | Solid catalyst for glycerol oxidation and preparation method thereof |
| CN111545239B (en) * | 2020-05-29 | 2021-06-25 | 江南大学 | Solid catalyst for glycerol oxidation and preparation method thereof |
| CN113995837A (en) * | 2021-11-05 | 2022-02-01 | 中国科学院长春应用化学研究所 | Template-free hollow tannic acid-iron nano coordination sphere and preparation method and application thereof |
| CN113995837B (en) * | 2021-11-05 | 2023-06-06 | 中国科学院长春应用化学研究所 | Template-free hollow tannic acid-iron nano coordination sphere and preparation method and application thereof |
| CN115350721A (en) * | 2022-10-21 | 2022-11-18 | 农业农村部环境保护科研监测所 | Nickel-based double-active-domain catalyst and preparation method and application thereof |
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