CN107469819B - Supported catalyst for preparing cyclohexene by benzene hydrogenation and preparation method thereof - Google Patents
Supported catalyst for preparing cyclohexene by benzene hydrogenation and preparation method thereof Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 39
- 239000002121 nanofiber Substances 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 34
- 239000000835 fiber Substances 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229920002521 macromolecule Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000011686 zinc sulphate Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- -1 ruthenium compound ruthenium nitrate Chemical class 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B01J35/23—
-
- B01J35/399—
-
- B01J35/58—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a supported catalyst for preparing cyclohexene by benzene hydrogenation and a preparation method thereof, wherein the catalyst comprises an active component Ru, a transition metal element Zn and a carbon nanofiber carrier, and the mass percentages of the components are that Ru is 1.0 wt% -15.0 wt% of carbon nanofiber and Zn is 0.1 wt% -10.0 wt% of Ru. Firstly, preparing the macromolecular nano-fiber containing the ruthenium compound and the transition metal compound by using an electrostatic spinning process, and then, carrying out high-temperature carbonization and hydrogen reduction to finally obtain the carbon nano-fiber serving as a carrier. Compared with the prior art, the catalyst has the advantages of higher activity and selectivity and the like.
Description
Technical Field
The invention relates to a supported catalyst, in particular to a supported catalyst for preparing cyclohexene by benzene hydrogenation and a preparation method thereof.
Background
Cyclohexene has an active double bond, is an important organic synthesis intermediate, and is widely applied to the production of fine chemicals such as adipic acid, nylon-6, nylon-66 and the like. Cyclohexene and its downstream products have important industrial application and broad market prospect.
Currently, nylon-6 and nylon-66 mainly adopt a complete benzene hydrogenation route, namely a route for producing cyclohexane by complete hydrogenation of benzene and oxidizing the cyclohexane to generate cyclohexanol and cyclohexanone. Cyclohexane oxidation belongs to free radical reaction, is easy to explode, and has the problems of long process flow, low yield, high energy consumption and easy environmental pollution. In contrast, cyclohexene is prepared by adopting a benzene partial hydrogenation route, and then cyclohexanol is prepared by hydrating cyclohexene, and the cyclohexanone and adipic acid are obtained by oxidizing the cyclohexanol. The key of the selective hydrogenation route of benzene lies in the preparation of the catalyst, in 1989, the industrialization of the selective hydrogenation process of benzene is realized in the water island at the Asahi formation rate in Japan, and the Asahi formation is still monopolized in the field of the catalyst for preparing cyclohexene by benzene hydrogenation.
At present, when the industrial operation index is 40% of benzene conversion, the selectivity and the yield of cyclohexene are respectively about 80% and 32%. However, the ruthenium catalyst produced by the Asahi formation is expensive, and the separation of the nano-scale catalyst from the product is difficult. Therefore, most of domestic and foreign patents adopt various carrier-supported catalysts (CN 100496728C, CN 1978053B, CN 103785477A, CN 103721709A, CN 101219391A, CN 101549292B and CN 102600888A) such as Al2O3, SiO2, ZrO2, MCM-41, SBA-15 and the like, and aim to solve the problem that the separation of the catalyst and the product is difficult to separate and further reduce the industrial production cost. However, the carrier has the problems of complex preparation process, high price and the like, and the obtained catalyst has low selectivity to cyclohexene, low activity and short service life. The carbon nanofiber obtained by electrostatic spinning is a carrier with a high specific surface area, the electrostatic spinning process is simple, the price is low, and reports about loading Ru on the carbon nanofiber do not exist at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a supported catalyst for preparing cyclohexene by benzene hydrogenation and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: the supported catalyst for preparing cyclohexene by benzene hydrogenation is characterized by comprising an active component Ru, a transition metal element Zn and a carbon nanofiber carrier, wherein the active component Ru accounts for 1.0-15.0 wt% of carbon nanofibers, and the active component Zn accounts for 0.1-10.0 wt% of Ru. The ranges of the amounts of Ru and Zn depend on the respective dispersibility, Ru is a noble metal, the amount of the supported Ru is reduced as much as possible while ensuring the activity, and Zn is used to improve the hydrophilicity of Ru in order to reduce the cost, so that the better the dispersibility of Zn in Ru, the smaller the amount is, and conversely, the larger the amount is, the better the dispersibility is.
Preferably, the Ru accounts for 5-10% of the carbon nano fiber, and the Zn accounts for 1.0-5.0 wt% of the Ru.
Preferably, the active component Ru and the transition metal element are present in a metallic state.
Preferably, the diameter of the carbon nanofiber carrier is 50-500 nm.
The preparation method of the supported catalyst for preparing cyclohexene by benzene hydrogenation is characterized by comprising the following steps:
a. under the condition of stirring, dissolving a macromolecule in a solvent, then adding an active component precursor ruthenium compound and a cocatalyst precursor transition metal compound into a macromolecule solution, and continuously stirring and ultrasonically treating to obtain a uniformly mixed solution A;
b. transferring the solution A into an injector, and spinning on electrostatic spinning equipment to obtain a nano-scale fiber composite material containing a ruthenium compound and a transition metal compound;
c. drying the fiber composite material, transferring the fiber composite material into a tubular furnace, carbonizing the fiber composite material at the temperature of 500-800 ℃ for 10-120 min under the protection of nitrogen, and then reducing the fiber composite material for 1-4h at the temperature of 200-500 ℃ by hydrogen to obtain the Ru-Zn/C nanofiber composite material.
Preferably, the ruthenium compound is ruthenium trichloride, ruthenium nitrate, ruthenium dichloro tricarbonyl dimer or ruthenium acetylacetonate;
preferably, the transition metal compound is ZnCl2、ZnSO4And Zn (NO)3)2；
Preferably, the polymer is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polycaprolactone or polyethylene oxide. The polymers have spinnability, and can maintain skeleton structure after carbonization.
The solvent comprises ethanol.
Further preferably, the ruthenium compound is ruthenium nitrate or ruthenium trichloride;
further preferably, the transition metal compound is zinc chloride;
more preferably, the polymer is polyvinyl alcohol or polyvinylpyrrolidone.
Preferably, the voltage of the regulating generator adopted by the electrostatic spinning is 5-50 kV; the influence factors of electrostatic spinning include voltage, receiving distance and extrusion rate of precursor solution, the spinning voltage is high, the extrusion speed can be faster, and the receiving distance can be shorter; the spinning voltage is low, the extrusion speed can be slower, the receiving distance can be longer, and the diameter and the surface appearance of the obtained yarn can be obviously different due to different receiving spinning conditions.
Preferably, the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 5-50 cm;
preferably, the extrusion speed of the precursor solution for electrostatic spinning is 0.006-0.2 mL/min.
Further preferably, the voltage of the regulating generator adopted by the electrostatic spinning is 5-30 kV;
further preferably, the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 5-25 cm;
further preferably, the extrusion speed of the electrospun precursor solution is 0.024-0.036 ml/min.
Still more preferably, the electrospinning precursor solution extrusion speed is 0.036-0.12 ml/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention mixes macromolecule, active component precursor and cocatalyst precursor and then carries out electrostatic spinning, wherein the macromolecule is changed into nanofiber under the action of electrostatic spinning, the active component and cocatalyst are dispersed in the nanofiber in the form of nano particles, and are embedded in carbon fiber in a physical form after high-temperature carbonization, so that the active component and cocatalyst are uniformly and firmly loaded on a carrier;
2. according to the invention, compounds of Ru and transition metal are uniformly dispersed in the polymer nano-fibers by adopting an electrostatic spinning process, and then the Ru-M/C nano-fibers are obtained through high-temperature carbonization and hydrogen reduction.
Drawings
FIG. 1 is a TEM spectrum of a sample prepared in example 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
5g PVP was dissolved in 10mL ethanol under magnetic stirring, and after sufficient dissolution, 0.5g RuCl was added3And 0.01g ZnCl2Stirring to dissolve, and transferring into injector. Adjusting the voltage of a generator to be 20kV, the receiving distance to be 15cm, the extrusion speed to be 0.08mL/min, and obtaining the nano-fiber through electrostatic spinning. Drying the fiber, and carbonizing at 550 ℃ for 30min in a vacuum tube furnace under the protection of nitrogen. And then reducing the carbonized fiber at 300 ℃ for 2h by hydrogen to finally obtain the carbon nanofiber loaded with metal Ru and Zn.
Example 2
Under magnetic stirring, 5g PVP was dissolved in 10 ethanol, and after sufficient dissolution, 1g RuCl was added3And 0.065g ZnCl2Stirring to dissolve, and transferring into injector. Adjusting the voltage of a generator to be 30kV, the receiving distance to be 25cm and the extrusion speed to be 0.12mL/min, and obtaining the nano-fiber through electrostatic spinning. Drying the fiber, and carbonizing at 550 ℃ for 30min in a vacuum tube furnace under the protection of nitrogen. And then reducing the carbonized fiber at 300 ℃ for 2h by hydrogen to finally obtain the carbon nanofiber loaded with metal Ru and Zn.
Example 3
Dissolving 5g PVP in 10 ethanol under magnetic stirring,after sufficient dissolution, 0.77g of RuCl was added3And 0.08g ZnCl2Stirring to dissolve, and transferring into injector. Adjusting the voltage of a generator to 10kV, the receiving distance to 10cm and the extrusion speed to 0.036mL/min, and obtaining the nanofiber through electrostatic spinning. Drying the fiber, and carbonizing at 550 ℃ for 30min in a vacuum tube furnace under the protection of nitrogen. And then reducing the carbonized fiber at 300 ℃ for 2h by hydrogen to finally obtain the carbon nanofiber loaded with metal Ru and Zn.
Example 4
5g of PVA was dissolved in 10g of water under magnetic stirring, and after sufficient dissolution, 0.78g of Ru (NO) was added3)2And 0.10g of ZnSO4Stirring to dissolve, and transferring into injector. Adjusting the voltage of a generator to be 15kV, the receiving distance to be 12cm and the extrusion speed to be 0.05mL/min, and obtaining the nano-fiber through electrostatic spinning. Drying the fiber, and carbonizing at 550 ℃ for 30min in a vacuum tube furnace under the protection of nitrogen. And then reducing the carbonized fiber at 300 ℃ for 2h by hydrogen to finally obtain the carbon nanofiber loaded with metal Ru and Zn.
Example 5
5g of PVA was dissolved in 10g of water under magnetic stirring, and after sufficient dissolution, 1.5g of Ru (NO) was added3)2And 0.2g of ZnSO4Stirring to dissolve, and transferring into injector. Adjusting the voltage of a generator to be 20kV, the receiving distance to be 15cm and the extrusion speed to be 0.06mL/min, and obtaining the nano-fiber through electrostatic spinning. Drying the fiber, and carbonizing at 550 ℃ for 30min in a vacuum tube furnace under the protection of nitrogen. And then reducing the carbonized fiber at 300 ℃ for 2h by hydrogen to finally obtain the carbon nanofiber loaded with metal Ru and Zn.
Determination of the activity and selectivity of the catalyst:
the activity and selectivity of the obtained catalyst are measured in a small-sized high-pressure reaction kettle. 0.5L autoclave, reaction system 150mL water, ZnSO4·7H221.60g of O, and the solid content in the slurry is 5.4g, wherein the content of Ru-Zn/C nano-fibers is 0.21 g. Replacing the air in the kettle with hydrogen, maintaining the hydrogen pressure at 4.0MPa, stirring at 800r/min, and heating at a rate120 ℃/h. When the temperature is raised to 140 ℃, the pretreatment is carried out for 10 hours. Then 80mL of benzene was added, and the hydrogen pressure was adjusted to 5.0MPa by starting the timer. Sampling every 5min, analyzing the content of benzene, cyclohexene and cyclohexane in the oil phase by a gas chromatograph, and then obtaining the corresponding conversion rate and cyclohexene selectivity.
TABLE 1 evaluation results of the Ru-Zn/C catalysts obtained in the different examples
| Catalyst and process for preparing same | Reaction time/min | Conversion rate/% | Selectivity/%) |
| Example 1 | 15 | 18.71 | 76.44 |
| Example 2 | 15 | 34.23 | 80.64 |
| Example 3 | 15 | 25.48 | 77.37 |
| Example 4 | 15 | 19.65 | 78.56 |
| Example 5 | 15 | 36.82 | 81.53 |
Example 6
The preparation method of the supported catalyst for preparing cyclohexene by benzene hydrogenation comprises the following steps:
a. under the condition of stirring, dissolving macromolecular polyvinylpyrrolidone in ethanol, then adding an active component precursor ruthenium compound ruthenium nitrate and a cocatalyst precursor transition metal compound zinc chloride into a macromolecular solution, and continuously stirring and ultrasonically treating to obtain a uniformly mixed solution A;
b. transferring the solution A into an injector, and spinning on electrostatic spinning equipment to obtain a nano-scale fiber composite material containing a ruthenium compound and a transition metal compound; the voltage of the regulating generator adopted by the electrostatic spinning is 5 kV; the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 5 cm; the extrusion speed of the precursor solution for electrostatic spinning is 0.006 mL/min.
c. Drying the fiber composite material, transferring the fiber composite material into a tubular furnace, carbonizing the fiber composite material at 500 ℃ for 10min under the protection of nitrogen, and then reducing the fiber composite material at 200 ℃ for 1h by hydrogen to obtain the Ru-Zn/C nanofiber composite material.
In the Ru-Zn/C nano-fiber composite material catalyst, Ru accounts for 1.0 wt% of the carbon nano-fibers, and Zn accounts for 0.1 wt% of the Ru.
The active component Ru and the transition metal element exist in a metal state.
The diameter of the carbon nanofiber carrier is 50 nm.
Example 7
The preparation method of the supported catalyst for preparing cyclohexene by benzene hydrogenation comprises the following steps:
a. in thatUnder the condition of stirring, high-molecular polyethylene oxide is dissolved in ethanol, and then active component precursor ruthenium compound ruthenium trichloride and cocatalyst precursor transition metal compound ZnSO4Adding the mixture into a polymer solution, and continuously stirring and ultrasonically treating the mixture to obtain a uniformly mixed solution A;
b. transferring the solution A into an injector, and spinning on electrostatic spinning equipment to obtain a nano-scale fiber composite material containing a ruthenium compound and a transition metal compound; the voltage of the regulating generator adopted by the electrostatic spinning is 50 kV; the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 50 cm; the extrusion speed of the precursor solution for electrostatic spinning is 0.2 mL/min.
c. Drying the fiber composite material, transferring the fiber composite material into a tubular furnace, carbonizing the fiber composite material at 800 ℃ for 120min under the protection of nitrogen, and then reducing the fiber composite material for 4h at 500 ℃ by hydrogen to obtain the Ru-Zn/C nanofiber composite material.
In the Ru-Zn/C nano-fiber composite material catalyst, Ru accounts for 15.0 wt% of the carbon nano-fibers, and Zn accounts for 10.0 wt% of the Ru.
The active component Ru and the transition metal element exist in a metal state.
The diameter of the carbon nanofiber carrier is 500 nm.
Example 8
The preparation method of the supported catalyst for preparing cyclohexene by benzene hydrogenation comprises the following steps:
a. dissolving high molecular polycaprolactone in ethanol under stirring, and then using ruthenium compound as active component precursor, dichlorotricarbonyl ruthenium dimer and cocatalyst precursor, transition metal compound Zn (NO)3)2Adding the mixture into a polymer solution, and continuously stirring and ultrasonically treating the mixture to obtain a uniformly mixed solution A;
b. transferring the solution A into an injector, and spinning on electrostatic spinning equipment to obtain a nano-scale fiber composite material containing a ruthenium compound and a transition metal compound; the voltage of the regulating generator adopted by the electrostatic spinning is 30 kV; the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 25 cm; the extrusion speed of the precursor solution for electrostatic spinning is 0.024 mL/min.
c. Drying the fiber composite material, transferring the fiber composite material into a tubular furnace, carbonizing the fiber composite material at 600 ℃ for 100min under the protection of nitrogen, and then reducing the fiber composite material at 300 ℃ for 2h by hydrogen to obtain the Ru-Zn/C nanofiber composite material.
In the Ru-Zn/C nano-fiber composite material catalyst, Ru accounts for 10.0 wt% of the carbon nano-fibers, and Zn accounts for 5.0 wt% of the Ru.
The active component Ru and the transition metal element exist in a metal state.
The diameter of the carbon nanofiber carrier is 100 nm.
Claims (9)
1. A preparation method of a supported catalyst for preparing cyclohexene by benzene hydrogenation is characterized in that a macromolecule, an active component precursor and a cocatalyst precursor are mixed and then subjected to electrostatic spinning, wherein the macromolecule is changed into nanofiber under the action of electrostatic spinning, the active component and the cocatalyst are dispersed in the nanofiber in a form of nanoparticles, and are embedded in carbon fiber in a physical form after high-temperature carbonization, so that the active component and the cocatalyst are uniformly and firmly supported on a carrier; the method specifically comprises the following steps:
a. under the condition of stirring, dissolving a macromolecule in a solvent, then adding an active component precursor ruthenium compound and a cocatalyst precursor transition metal compound into a macromolecule solution, and continuously stirring and ultrasonically treating to obtain a uniformly mixed solution A;
b. transferring the solution A into an injector, and spinning on electrostatic spinning equipment to obtain a nano-scale fiber composite material containing a ruthenium compound and a transition metal compound;
c. drying the fiber composite material, transferring the fiber composite material into a tubular furnace, carbonizing the fiber composite material at the temperature of 500-800 ℃ for 10-120 min under the protection of nitrogen, and then reducing the fiber composite material for 1-4h at the temperature of 200-500 ℃ by hydrogen to obtain the Ru-Zn/C nanofiber composite material;
the obtained Ru-Zn/C nano-fiber composite material is used as a catalyst, wherein Ru accounts for 1.0-15.0 wt% of the carbon nano-fiber, and Zn accounts for 0.1-10.0 wt% of the Ru.
2. The method for preparing the supported catalyst for preparing cyclohexene through benzene hydrogenation according to claim 1, wherein the Ru accounts for 5-10% of the carbon nanofibers, and the Zn accounts for 1.0-5.0 wt% of the Ru.
3. The method of claim 1, wherein the active component Ru and the transition metal element are present in the metallic form.
4. The method for preparing the supported catalyst for preparing cyclohexene through benzene hydrogenation according to claim 1, wherein the diameter of the carbon nanofiber carrier is 50-500 nm.
5. The method for preparing the supported catalyst for preparing cyclohexene by benzene hydrogenation according to claim 1, wherein the ruthenium compound is ruthenium trichloride, ruthenium nitrate, ruthenium dichlorotricarbonyl dimer or ruthenium acetylacetonate;
the transition metal compound is ZnCl2、ZnSO4And Zn (NO)3)2；
The polymer is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polycaprolactone or polyethylene oxide;
the solvent comprises ethanol.
6. The method for preparing the supported catalyst for preparing cyclohexene by benzene hydrogenation according to claim 5, wherein the ruthenium compound is ruthenium nitrate or ruthenium trichloride;
the transition metal compound is zinc chloride;
the polymer is polyvinyl alcohol or polyvinylpyrrolidone.
7. The method for preparing the supported catalyst for preparing cyclohexene through benzene hydrogenation according to claim 1, wherein the voltage of a regulating generator used for electrostatic spinning is 5-50 kV;
the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 5-50 cm;
the extrusion speed of the precursor solution for electrostatic spinning is 0.006-0.2 mL/min.
8. The method for preparing the supported catalyst for preparing cyclohexene through benzene hydrogenation according to claim 7, wherein the voltage of the generator used for electrostatic spinning is 5-30 kV;
the receiving distance of the electrostatic spinning is the distance between the spray head and the receiver, and the receiving distance is 5-25 cm;
the extrusion speed of the precursor solution for electrostatic spinning is 0.024-0.036 ml/min.
9. The method of claim 7, wherein the electrospinning precursor solution extrusion rate is 0.036-0.12 ml/min.
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| CN102861572A (en) * | 2012-10-12 | 2013-01-09 | 李建修 | Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene |
| CN104190417A (en) * | 2014-07-21 | 2014-12-10 | 复旦大学 | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene |
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| CN101455975A (en) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof |
| CN102861572A (en) * | 2012-10-12 | 2013-01-09 | 李建修 | Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene |
| CN104190417A (en) * | 2014-07-21 | 2014-12-10 | 复旦大学 | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene |
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