CN110013871A - Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material and its preparation method and application - Google Patents
Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material and its preparation method and application Download PDFInfo
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- CN110013871A CN110013871A CN201910311224.7A CN201910311224A CN110013871A CN 110013871 A CN110013871 A CN 110013871A CN 201910311224 A CN201910311224 A CN 201910311224A CN 110013871 A CN110013871 A CN 110013871A
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- nickel
- containing nitrogen
- support type
- composite catalyst
- catalyst
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 56
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 nitrogenous compound Chemical class 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to catalyst technical fields, and in particular to a kind of support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material and its preparation method and application.The catalyst includes nickel phosphide-nickel composite active center and containing nitrogen nano-material, it is prepared using equivalent impregnation method, utilize specific nitrogenous stabilizer, the inorganic salts of nickel, triphenylphosphine, N, dinethylformamide wiring solution-forming, drying and processing is carried out after impregnating well, obtained presoma is utilized into temperature programmed nitridation, reduction treatment obtains support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material, the catalyst activity component of preparation is evenly distributed, catalyst life is long, there is very high activity to dibenzofuran, there is very high selectivity to cyclohexyl benzene, with good prospects for commercial application.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of support type nickel phosphide-nickel/compound containing nitrogen nano-material
Catalyst and its preparation method and application.
Background technique
Cyclohexyl benzene is a kind of important chemical intermediate, can be used as anti-overcharge dose of lithium ion battery, is a kind of additional
It is worth big, the huge fine chemicals of market potential, it is domestic at present not yet to form large-scale production.The synthetic route of cyclohexyl benzene,
It is reacted including benzene hydrogenation alkylation, phenylbenzene moiety hydrogenation and benzene with the Friedel-Crafts of alkylating reagent.Wherein, using from
The available very high cyclohexyl benzene selectivity of the alkylated reaction of sub- liquid catalyst benzene and alkylating agent and yield, ionic liquid
Reusability and efficient catalytic performance become the green solvent of high-efficiency environment friendly a kind of, the method is deemed suitable for greatly
The synthetic route most with prospects of large-scale production cyclohexyl benzene.But as ionic liquid access times increase, under purity
Drop, catalytic effect reduce, and how economically to make ionic liquid regeneration is critical issue urgently to be resolved.In addition, ionic liquid is urged
Change technology many places in the laboratory lab scale stage, before industrial applications there are also higher cost, viscosity is larger, stability is inadequate, urges
Change many problems such as mechanism study deficiency to need to solve.
Dibenzofuran is white or light yellow crystal, and band blue-fluorescence has epoxy construction, not soluble in water, is dissolved in ethyl alcohol and second
Ether.There is the higher dibenzofuran of content in the fraction washing oil of coal tar, has the characteristics that be easily obtained and low in cost.Washing oil content
In it is more, dibenzofuran is extracted from washing oil, can not only obtain the dibenzofuran product of high value, and can be improved washing oil washes benzene
Can, it is also beneficial to separate other components from washing oil.It is domestic at present less to the component exploitation in washing oil product, dibenzofuran is answered
It is also less with studying.
Summary of the invention
In view of the shortcomings of the prior art and disadvantage, the present invention is using relatively inexpensive support type nickel phosphide-nickel/nitrogenous
Nano material composite catalyst carries out hydrogenation deoxidation research to dibenzofuran.The present invention uses phosphorus-containing compound for phosphorus source, nickeliferous chemical combination
Object is nickel source, and nitrogenous compound is the nitrogen source for adulterating nitrogenous nano-sized carbon.It is set to generate the complex of different ratio by solvent, into
Row impregnation is made presoma by drying, then carries out high temperature reduction cracking again, and available support type nickel phosphide-nickel/
Composite catalyst containing nitrogen nano-material.Catalyst obtained includes nickel phosphide-nickel composite active center, contains nitrogen nano-material,
Wherein, the content containing nitrogen nano-material is determined according to the additional amount of containing n-donor ligand；Nickel phosphide-nickel accounts for the 5% of catalyst gross mass
~50%.
The present invention is the target of hydrogenation deoxidation with dibenzofuran (important crude oil byproduct), utilizes the support type phosphatization of synthesis
Nickel-nickel/composite catalyst containing nitrogen nano-material has studied property of the catalyst of the present invention for dibenzofuran hydrogenation deoxidation as catalyst
It can influence, it is found that catalyst of phosphatizing nickel prepared by the present invention has very high selectivity to cyclohexyl benzene.
Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material of the present invention is the preparation method comprises the following steps: using isometric leaching
The salting liquid of phosphorous compound and nickel is supported on the carrier of catalyst and by nitrogenous compound fabricated in situ by stain method
The nickel phosphide containing nitrogen nano-material is adulterated, by impregnation drying, the available load nickel phosphide-nickel/of thermal cracking reduction treatment contains
Nitrogen nano-material composite catalyst.
Specific step is as follows for the equi-volume impregnating of the catalyst:
(1), the carrier for weighing known water absorption rate, the baking oven progress drying and processing for being put into certain temperature are spare；
(2), by Ni (NO3)2·6H2O and phosphorus-containing compound, containing n-donor ligand, which are dissolved in N,N-dimethylformamide (DMF), to be obtained
To solution, by solution left standstill 1-6h；
(3), the solution that step (2) are prepared is instilled dropwise on the carrier of step (1), carries out incipient impregnation, then exists
Sealing is placed 12-24 hours at room temperature, drying, spare；
(4), step (3) solid is put into reduction apparatus (reduction tube) and carries out reduction treatment, catalyst can be obtained.
Wherein, the carrier of above-mentioned preparation method step (1) load is SBA-15, SiO2, Al2O3, in mesoporous carbon one
Kind；Existing commercial goods can be bought, can also be prepared by the corresponding equipment of document utilization；The drying condition are as follows: 70
Dry 2-12h under DEG C -130 DEG C of environment.
The step (2) is that 0.1-3g melamine and 0.1-3g triphenylphosphine are dissolved in 5-10mLDMF, then by Ni
(NO3)2.6H2O is added thereto, and makes molar ratio n (P): n (Ni)=0:1-10:1 of phosphorus, nickel；It is configured to solution, it is spare；
Since catalyst precursor belongs to metal organic framework compound, the condition existing for containing n-donor ligand and phosphorus-containing ligand
Under, high temperature reduction carries out fabricated in situ, and nitrogenous nano material is introduced after having restored, and prepared catalyst is reducing also
While former temperature, make the more uniform of Active components distribution；Because introducing nitrogenous nano material, alkalinity abundant is provided
Site, and generate together with active component the catalytic effect of collaboration, can make to be catalyzed use temperature range and broaden.
Drying condition described in step (3) are as follows: dry 1-12h at 80-120 DEG C in oil bath；
Support type nickel phosphide-nickel of reduction synthesis described in step (the 4)/condition of composite catalyst containing nitrogen nano-material are as follows:
150 DEG C -650 DEG C are risen to from room temperature with the temperature rate of 1-5 DEG C/min under the atmosphere of nitrogen, 2-6h is kept, then switches to
Continue to keep 2-6h under the atmosphere of hydrogen.
Support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material produced by the present invention be used for using dibenzofuran as raw material,
Under solvent and catalyst existence condition, addition hydrogen carries out catalysis reaction and prepares cyclohexyl benzene.
Preferably, the catalytic reaction condition are as follows: reaction temperature is 200-400 DEG C, Hydrogen Vapor Pressure 1-4MPa；Instead
The liquid hourly space velocity (LHSV) (LHSV) for answering raw material is 0.2-10h-1；Catalyst amount is 0.1-1g；The solvent is decane, hexamethylene
The mass ratio of alkane, benzene, dibenzofuran and solvent is 3: 100-5: 100.
Technical effect of the invention: compared with prior art, catalyst of the present invention is used to have such as dibenzofuran hydrogenation deoxidation
Lower advantage:
1, the catalyst carrier in the present invention selects SBA-15, SiO2, Al2O3, mesoporous carbon, the model of catalyst carrier selection
Wide, the high conversion rate of dibenzofuran is enclosed, the selectivity of cyclohexyl benzene is high.
2, because active component is to exist in the form of complex compound when not restoring, carrier table can be uniformly dispersed in
Face, and reduction temperature is lower, so catalyst is uniformly dispersed, particle very little.
3, for this catalyst activity high reaction temperature only between 150 DEG C -650 DEG C, it is raw that active section is more advantageous to greatly chemical industry
The progress of production.
4, this catalyst can sulfur resistive, containing a small amount of sulphur raw material in still have very high catalytic activity.
5, load nickel phosphide-nickel/composite catalyst containing nitrogen nano-material is not only cheap, but also has good plus hydrogen
Deoxidation effect prepares cyclohexyl benzene by dibenzofuran plus hydrogen, has good economy and industrial value.Solving catalyst cannot hold
It utilizes long, the high drawback of cost of manufacture.
6, using one-step synthesis method nickel phosphide, simple process is small to equipment injury, and discharge amount of exhaust gas is minimum.
Specific embodiment
Below by specific embodiment, the present invention will be described in detail.
Embodiment 1
The preparation of catalyst:
The water absorption rate for determining mesoporous SBA-15 first, dries by 100 DEG C, then accurately weighs the mesoporous silicon oxide of 1g
It is spare as carrier, by 0.77gNi (NO3)2·6H2O and 0.35g triphenylphosphine (PPh3), 0.64g melamine are dissolved in 10ml
Solution is obtained in n,N-Dimethylformamide (DMF), by solution left standstill 1h (ligand needs the regular hour when being complexed).
Then ready meso-porous titanium dioxide silicon carrier is instilled dropwise, carries out equivalent impregnation, and then sealing is put at room temperature
It sets 12 hours, then moves into 90 DEG C and drying and processing is carried out by bath, obtain the presoma of catalyst, presoma is moved into reduction tube
Among, 550 DEG C are risen to from room temperature with the temperature rate of 2.5 DEG C/min under the atmosphere of nitrogen, 3h is kept, then switches to hydrogen
Atmosphere under continue keep 3h.Obtain support type nickel phosphide-nickel/nitrogenous nanometer that catalyst activity component mass fraction is 20%
Silica composite catalyst.
The catalyst for restoring and being passivated is weighed 0.2 gram to be put into fixed bed reactors, adjusts the liquid space-time of raw material
Rate (WHSV), holding Hydrogen Vapor Pressure are 2MPa, and hydrogen flowing quantity 60ml/min makes heating furnace heat up, from room temperature with 5 DEG C/min
200 DEG C are risen to, different reaction temperatures can be set, finally take out reaction product, analyzed using gas-chromatography.
Embodiment 2
With 0.37gNi (NO3)2·6H2O replaces 0.77gNi (NO in embodiment 13)2·6H2O, other same embodiments of step
1。
Embodiment 3
With 0.17gNi (NO3)2·6H2O replaces 0.77gNi (NO in embodiment 13)2·6H2O, other same embodiments of step
1。
Embodiment 4
With 0.97gNi (NO3)2·6H2O replaces 0.77gNi (NO in embodiment 13)2·6H2O, other same embodiments of step
1。
Embodiment 5
0.35g triphenylphosphine (PPh3) in embodiment 1 is replaced with 0.15g triphenylphosphine (PPh3), other steps are the same as implementation
Example 1.
Embodiment 6
0.35g triphenylphosphine (PPh3) in embodiment 1 is replaced with 0.55g triphenylphosphine (PPh3), other steps are the same as implementation
Example 1.
Embodiment 7
0.35g triphenylphosphine (PPh3) in embodiment 1 is replaced with 0.05g triphenylphosphine (PPh3), other steps are the same as implementation
Example 1.
Embodiment 8
0.35g triphenylphosphine (PPh3) in embodiment 1 is replaced with 0.45g triphenylphosphine (PPh3), other steps are the same as implementation
Example 1.
The quality of different phosphorus-containing ligands is mainly investigated out above to the controllable of catalyst activity component nickel phosphide and nickel ratio
Property, there is good research potential.
Embodiment 9
0.35g ammonium phosphite replaces 0.35g triphenylphosphine (PPh3) in embodiment 1, and other steps are the same as embodiment 1.
Embodiment 10
0.35g phosphoric acid replaces 0.35g triphenylphosphine (PPh3) in embodiment 1, and other steps are the same as embodiment 1.
Embodiment 11
0.35g nickel phosphate replaces 0.35g triphenylphosphine (PPh3) in embodiment 1, and other steps are the same as embodiment 1.
Embodiment 12
10ml n,N-Dimethylformamide (DMF) in embodiment 1 is replaced with 10ml ethyl alcohol, other steps are the same as embodiment 1.
Embodiment 13
10ml n,N-Dimethylformamide (DMF) in embodiment 1, other same embodiments of step are replaced with 10ml decane
1。
Embodiment 14
10ml n,N-Dimethylformamide (DMF) in embodiment 1, other same embodiments of step are replaced with 10ml triethylamine
1。
Embodiment 15
1 intermediary hole SBA-15 of embodiment is replaced with active carbon, other steps are the same as embodiment 1.
Embodiment 16
Use SiO2Instead of 1 intermediary hole SBA-15 of embodiment, other steps are the same as embodiment 1.
Embodiment 17
Use Al2O3Instead of 1 intermediary hole SBA-15 of embodiment, other steps are the same as embodiment 1.
Embodiment 18
" atmosphere of nitrogen " replaces " atmosphere of hydrogen " in embodiment 1 in the preparation of catalyst.Other steps are the same as implementation
Example 1.
Embodiment 19
In catalyst preparation, by " rising to 500 DEG C from room temperature with 5 DEG C/min " surrogate response example, " from room temperature with 5
DEG C/min rises to 200 DEG C ".Other steps are the same as embodiment 1.
Embodiment 20
In catalyst preparation, by " rising to 400 DEG C from room temperature with 5 DEG C/min " surrogate response example, " from room temperature with 5
DEG C/min rises to 200 DEG C ".Other steps are the same as embodiment 1.
Embodiment 21
In catalyst preparation, by " rising to 300 DEG C from room temperature with 5 DEG C/min " surrogate response example, " from room temperature with 5
DEG C/min rises to 200 DEG C ".Other steps are the same as embodiment 1.
Embodiment 22
Catalyst in embodiment 1 is run into 300h, is then analyzed using gas-chromatography.
Comparative example 1
By 0.77gNi (NO3)2·6H2O, which is dissolved in 10ml n,N-Dimethylformamide (DMF), obtains solution, and solution is quiet
It sets.Then ready meso-porous titanium dioxide silicon carrier is instilled dropwise, carries out equivalent impregnation, and then sealing placement 12 is small at room temperature
When, then move into 90 DEG C and drying and processing is carried out by bath, the presoma of catalyst is obtained, presoma is moved among reduction tube,
It is passed through H2Reduction, is then cooled to phosphatization temperature, prepared triphenylphosphine solution is transported to fixed bed with high pressure constant flow pump
Phosphatization in reactor,
The catalyst for restoring and being passivated is weighed 0.2 gram to be put into fixed bed reactors, adjusts the liquid space-time of raw material
Rate (WHSV), holding Hydrogen Vapor Pressure are 2MPa, and hydrogen flowing quantity 60ml/min makes heating furnace heat up, from room temperature with 5 DEG C/min
200 DEG C are risen to, different reaction temperatures can be set, finally take out reaction product, analyzed using gas-chromatography.
Each embodiment of table 1 compares the performance of dibenzofuran hydrogenation deoxidation
Table 1 illustrates that the method for the present invention is obtained and loads nickel phosphide-nickel/composite catalyst containing nitrogen nano-material, to dibenzofuran
Hydrogenation deoxidation performance reactivity with higher, and to cyclohexyl benzene selectivity with higher,
It should be appreciated that for those of ordinary skills, improvements and changes can be subject to according to the above description, and institute
The such modifications and variations of progress should all belong to scope of protection of the claims.
Claims (8)
1. a kind of support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material preparation method, it is characterised in that: the system
Steps are as follows for Preparation Method:
(1), it is spare to be put into baking oven progress drying and processing for the carrier for weighing known water absorption rate；
(2), by Ni (NO3)2·6H2O be dissolved in N,N-dimethylformamide (DMF) with phosphorus-containing compound, containing n-donor ligand obtain it is molten
Liquid, and by solution left standstill 1-6h；
(3), the solution after standing step (2) is instilled dropwise on the carrier of step (1), incipient impregnation is carried out, then in room
The lower sealing of temperature is placed 12-24 hours, is then dried, spare；
(4), the solid of step (3) is put into reduction apparatus and carries out reduction treatment, catalyst can be obtained.
2. support type nickel phosphide as described in claim 1-nickel/composite catalyst containing nitrogen nano-material preparation method, special
Sign is: step (1) carrier is SBA-15, SiO2, Al2O3, one of mesoporous carbon；The drying condition are as follows: 70 DEG C-
Dry 2-12h under 130 DEG C of environment.
3. support type nickel phosphide as described in claim 1-nickel/composite catalyst containing nitrogen nano-material preparation method, special
Sign is: the step (2) is that 0.1-3g melamine and 0.1-3g triphenylphosphine are dissolved in 5-10m LDMF, then by Ni
(NO3)2.6H2O is added thereto, and is made molar ratio n (P): n (Ni)=0:1-10:1 of phosphorus and nickel, is configured to solution, spare.
4. support type nickel phosphide as described in claim 1-nickel/composite catalyst containing nitrogen nano-material preparation method, special
Sign is: drying condition described in step (3) are as follows: dry 1-12h at 80-120 DEG C in oil bath.
5. support type nickel phosphide as described in claim 1-nickel/composite catalyst containing nitrogen nano-material preparation method, special
Sign is: the condition of composite catalyst is restored described in step (4) are as follows: with the temperature speed of 1-5 DEG C/min under the atmosphere of nitrogen
Rate rises to 150 DEG C -650 DEG C from room temperature, keeps 2-6h, then switches to and continues to keep 2-6h under the atmosphere of hydrogen.
6. a kind of support type nickel phosphide-nickel/composite catalyst containing nitrogen nano-material of method preparation as claimed in claim 2 is answered
With, it is characterised in that: the catalyst is used for using dibenzofuran as raw material, and under solvent and catalyst existence condition, hydrogen is added
It carries out catalysis reaction and prepares cyclohexyl benzene.
7. support type nickel phosphide as claimed in claim 6-nickel/composite catalyst containing nitrogen nano-material application, feature exist
In: the catalytic reaction condition are as follows: reaction temperature is 200-400 DEG C, Hydrogen Vapor Pressure 1-4MPa；The liquid space-time of reaction raw materials
Fast (LHSV) is 0.2-10h-1。
8. support type nickel phosphide as claimed in claim 6-nickel/composite catalyst containing nitrogen nano-material application, feature exist
In: the catalyst amount is 0.1-1g；The solvent is decane, hexamethylene, benzene, and the mass ratio of dibenzofuran and solvent is 3:
100-5∶100。
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