CN116283738A - Method for synthesizing 2,2' -bipyridine by using composite catalyst - Google Patents
Method for synthesizing 2,2' -bipyridine by using composite catalyst Download PDFInfo
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- CN116283738A CN116283738A CN202310245281.6A CN202310245281A CN116283738A CN 116283738 A CN116283738 A CN 116283738A CN 202310245281 A CN202310245281 A CN 202310245281A CN 116283738 A CN116283738 A CN 116283738A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000010926 purge Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for synthesizing 2,2' -bipyridine by using a composite catalyst, and relates to the technical field of chemical synthesis; preparing a composite catalyst: taking a nickel compound as a catalytic active ingredient, selecting porous carbon as a carrier, taking organic alcohols as a solvent, preparing homogenate of a composite catalyst by using a homogenate method, adding a dispersing agent accounting for 1-10% of the mass of the porous carbon into the homogenate, centrifuging and granulating to obtain composite catalyst microspheres, calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, and synthesizing 2,2' -bipyridine: pyridine enters a fixed bed layer of the composite catalyst microsphere under nitrogen purging to carry out coupling reaction to obtain a crude product, and 2,2' -bipyridine is obtained through purification; the whole preparation process flow of the 2,2' -bipyridine is optimized, and the production cost is reduced.
Description
Technical Field
The invention discloses a method, relates to the technical field of chemical synthesis, and in particular relates to a method for synthesizing 2,2' -bipyridine by using a composite catalyst.
Background
The 2,2' -bipyridine is one of bipyridine isomers, is an important organic synthesis intermediate, is mainly used for medical intermediates, organic synthesis and the like, and is also widely applied to chelating agents and paint additives, and is applied to dye production, pesticide production, perfume and the like.
The existing method for synthesizing 2,2 '-bipyridine mainly comprises two methods, namely Ullmann method, taking 2-halogenated pyridine as raw material, and performing coupling reaction under the action of catalyst to generate 2,2' -bipyridine, wherein the method is difficult to prepare and high in price, and meanwhile, the requirement on reaction equipment is strict due to corrosiveness of halogen elements; the other is to use Raney nickel as a catalyst and pyridine as a raw material to synthesize the 2,2' -bipyridine, wherein the Raney nickel powder of the catalyst has higher chemical activity, is easy to generate oxidation reaction and even spontaneous combustion when exposed in air, has great potential safety hazard, and is easy to poison in the reaction, so that the service life of the catalyst is relatively short, and the consumption and production cost are increased.
Pyridine is used as a raw material, and a composite catalyst is used for synthesizing 2,2 '-dipyridine, so that the method is a main method for producing 2,2' -dipyridine at home and abroad at present. Therefore, the composite catalyst with high activity, strong toxicity resistance and easy preparation is particularly important for optimizing the whole process flow and controlling the cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing 2,2 '-bipyridine by using a composite catalyst, which is used for synthesizing 2,2' -bipyridine, has high activity, strong toxicity resistance and easy preparation, optimizes the whole process flow and reduces the production cost.
The specific scheme provided by the invention is as follows:
the invention provides a method for synthesizing 2,2' -bipyridine by a composite catalyst,
the preparation of the composite catalyst comprises taking nickel compound as catalytic active component, selecting porous carbon with a mass ratio of Kong Zhanbi% -30%, mesoporous content of 20-50% and micropore content of 10-35% as carrier, taking organic alcohol as solvent, wherein the mass content of nickel compound is 1% -30% of porous carbon, the mass ratio of organic alcohol to porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; preserving heat at 450 ℃ for 60min;
synthesis of 2,2' -bipyridine: pyridine enters a fixed bed layer of the composite catalyst microsphere under nitrogen purging to carry out coupling reaction to obtain a crude product, and 2,2' -bipyridine is obtained through purification.
More preferably, the nickel compound is present in an amount of 5 to 25% by mass, more preferably 10 to 15% by mass, based on the mass of the porous carbon.
Preferably, the addition amount of the dispersing agent is 3-8% of the mass of the porous carbon, and more preferably, the addition amount of the dispersing agent is 5-7% of the mass of the porous carbon.
Preferably, the slurry has a solids content of 45-60%, more preferably 50-55%.
Preferably, in the method for synthesizing 2,2' -bipyridine by using the composite catalyst, the nickel compound comprises one or more of nickel nitrate, nickel dichloride hexahydrate and nickel sulfate.
Preferably, in the method for synthesizing the 2,2' -bipyridine by using the composite catalyst, porous carbon with the size of Kong Zhanbi-25%, the medium of Kong Zhanbi-45% and the micropore ratio of 15-25% is selected as a carrier. More preferably, porous carbon with a pore ratio of 15-25% is selected from the group consisting of Kong Zhanbi% -25%, kong Zhanbi% -45% and micropores. Porous carbon is used as a carrier, so that the finite field reaction in the catalyst reaction can be realized, and the two-phase interface diffusion contact reaction in the catalytic reaction process can be regulated and controlled efficiently.
Preferably, in the method for synthesizing the 2,2' -bipyridine by using the composite catalyst, porous carbon with specific surface area BET of 100-1000m < 2 >/g is selected as a carrier. More preferably, porous carbon having a BET of 150 to 700m2/g is used as a carrier, and still more preferably, porous carbon having a BET of 240 to 500m2/g is used as a carrier.
Preferably, in the method for synthesizing the 2,2' -bipyridine by using the composite catalyst, the dispersing agent is a zwitterionic surfactant, and comprises one or more of alcohol ether phosphate, betaine type amphoteric surfactant and laureth potassium phosphate. More preferably, the laureth phosphate potassium with easy water dissolution and good acid-base stability is used as the dispersing agent.
Preferably, the organic alcohol comprises one or a mixture of methanol and ethanol.
Is prepared by granulating
Is preferably +.>
More preferably +.>
Is a composite catalyst microsphere.
Preferably, in the method for synthesizing the 2,2' -bipyridine by using the composite catalyst, pyridine with the feeding flow rate of 0.02-0.4ml/min enters a fixed bed layer of the composite catalyst microsphere for coupling reaction under the nitrogen purging with the flow rate of 60-200ml/min at the reaction temperature of 120-200 ℃.
Preferably, the reaction temperature of pyridine with the composite catalyst is 140-180 ℃, and more preferably 150-170 ℃.
Preferably, the nitrogen flow rate is 80-160ml/min, and more preferably 100-140ml/min.
Preferably, the pyridine feed flow rate is from 0.05 to 0.3ml/min, and more preferably from 0.1 to 0.2ml/min.
The invention also provides a preparation method of the composite catalyst, which comprises the following steps: taking nickel compound as a catalytic active component, selecting porous carbon with a mass ratio of Kong Zhanbi% -30%, a mesoporous ratio of 20-50% and a micropore ratio of 10-35% as a carrier, taking organic alcohol as a solvent, wherein the mass content of the nickel compound is 1% -30% of the mass of the porous carbon, the mass ratio of the organic alcohol to the porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; the temperature is kept at 450 ℃ for 60min.
The invention also provides a composite catalyst, which is prepared by the preparation method of the composite catalyst.
The invention has the advantages that:
the invention provides a method for synthesizing 2,2 '-bipyridine by a composite catalyst, which is characterized in that the composite catalyst is prepared, and the 2,2' -bipyridine is prepared by the composite catalyst, the invention adopts a high-efficiency homogenate method, porous carbon with a certain hole proportion is used as a carrier, active nickel is loaded under the participation of a solvent, the homogenate is centrifuged and granulated to prepare composite catalyst microspheres, and the microspheres are calcined under a certain temperature to obtain a finished product composite catalyst for better solidifying the active nickel, so that the pyridine conversion rate is further improved, the raw materials are cheap and easily available, the preparation cost of the composite catalyst can be effectively reduced, and the composite catalyst has toxicity resistance and is suitable for recycling; when the method of the invention uses the composite catalyst to prepare the 2, 2-bipyridine, the operation is simple, the reaction condition is mild, the single conversion rate of the pyridine is high, the conversion rate of the pyridine is further improved, and the method is beneficial to industrial production.
Drawings
FIG. 1 is a schematic illustration of the process flow of the method of the present invention.
Fig. 2 is a schematic view of the specific surface area of porous carbon according to the present invention.
FIG. 3 is a schematic representation of a porous carbon specific surface profile in accordance with the present invention.
Fig. 4 is a schematic diagram of pore volume-pore diameter of porous carbon according to the present invention.
FIG. 5 is a schematic diagram of the pore volume-pore diameter integrated distribution curve of the porous carbon according to the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a method for synthesizing 2,2' -bipyridine by using a composite catalyst, which is prepared by taking a nickel compound as a catalytic active component, selecting porous carbon with a large Kong Zhanbi-30%, a mesoporous content of 20-50% and a micropore content of 10-35% as a carrier, taking organic alcohol as a solvent, wherein the mass content of the nickel compound is 1-30% of the mass of the porous carbon, the mass ratio of the organic alcohol to the porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; preserving heat at 450 ℃ for 60min;
synthesis of 2,2' -bipyridine: pyridine enters a fixed bed layer of the composite catalyst microsphere under nitrogen purging to carry out coupling reaction to obtain a crude product, and 2,2' -bipyridine is obtained through purification.
The composite catalyst prepared by the method is used for synthesizing 2,2' -bipyridine. Reference may be made to some preferred embodiments of the method of the invention for specific applications. The content of substances which are not specifically described in the embodiment of the method is in parts by mass (m/m).
Example 1:
synthesis of composite catalyst: adding about 10% of the mixture with a size of Kong Zhanbi, about 35% of the mixture with Kong Zhanbi, a micropore ratio of about 55% and a specific surface area of about 1000m into a homogenizer 2 1 part of per g carrier porous active carbon, adding 2 parts of ethanol, dispersing uniformly, adding 0.3 part of active component nickel nitrate again, dispersing again, adding 0.1 part of dispersant betaine, fully homogenizing and dispersing to uniformity, centrifuging at high speed until the solid content is about 65%, and granulating to obtain the product
About 5mm, and then performing calcination according to the temperature of the temperature curve RT-100 ℃,30min,100-300 ℃,60min,300-450 ℃,60min and 450 ℃ for 60min to obtain a spherical composite catalyst;
synthesis of 2,2' -bipyridine: 30g of the composite catalyst is added on a fixed bed, the nitrogen flow rate is 200ml/min, the pyridine feeding flow rate is 0.4ml/min, the reaction temperature is 200 ℃,2' -bipyridine is obtained through post-treatment, the single conversion rate of pyridine can reach 7.2% through calculation, and the crude product is recrystallized to obtain white solid 2, 2-bipyridine, wherein the purity reaches 99.2%.
Example 2:
synthesis of composite catalyst: adding about 30% of the mixture with a size of Kong Zhanbi, 50% of mesopores, 20% of micropores and a specific surface area of about 100m into a homogenizer 2 1 part of per g carrier porous active carbon, adding 1.7 parts of methanol, dispersing uniformly, adding 0.01 part of active component nickel dichloride hexahydrate again, dispersing again, adding 0.01 part of dispersant betaine, fully homogenizing and dispersing uniformly, centrifuging at high speed until the solid content is about 40%, and granulating to obtain the product
About 1mm, and then performing calcination according to the temperature of the temperature curve RT-100 ℃,30min,100-300 ℃,60min,300-450 ℃,60min and 450 ℃ for 60min to obtain a spherical composite catalyst;
synthesis of 2,2' -bipyridine: 30g of the composite catalyst is added on a fixed bed, the nitrogen flow rate is 60ml/min, the pyridine feeding flow rate is 0.2ml/min, the reaction temperature is 120 ℃,2' -bipyridine is obtained through post-treatment, the conversion rate of pyridine can reach 8.4% through calculation, and the crude product is recrystallized to obtain white solid 2, 2-bipyridine, wherein the purity reaches 99.1%.
Example 3:
synthesis of composite catalyst: adding about 25% of the mixture with a size of Kong Zhanbi, 40% of mesopores, 32% of micropores and a specific surface area of about 320m into a homogenizer 2 1 part of per gram of carrier porous active carbon, 1.4 parts of ethanol is added, and after uniform dispersion, the mixture is subjected toAdding 0.12 part of active component nickel sulfate, dispersing again, adding 0.06 part of dispersing agent lauryl alcohol ether phosphate, fully homogenizing and dispersing until uniform, centrifuging at high speed until the solid content is about 53%, and granulating to obtain the final product
About 3mm, and then performing calcination according to the temperature of the temperature curve RT-100 ℃,30min,100-300 ℃,60min,300-450 ℃,60min and 450 ℃ for 60min to obtain a spherical composite catalyst;
synthesis of 2,2' -bipyridine: 30g of the composite catalyst is added on a fixed bed, the nitrogen flow rate is 120ml/min, the pyridine feeding flow rate is 0.5ml/min, the reaction temperature is 160 ℃,2' -bipyridine is obtained through post-treatment, the conversion rate of pyridine can reach 9.6% through calculation, and the crude product is recrystallized to obtain white solid 2, 2-bipyridine, wherein the purity reaches 99.3%.
Example 4:
synthesis of composite catalyst: adding about 25% of the mixture with a size of Kong Zhanbi, 40% of mesopores, 32% of micropores and a specific surface area of about 320m into a homogenizer 2 1 part of per g carrier porous active carbon, adding 1.4 parts of ethanol, dispersing uniformly, adding 0.12 part of active component nickel nitrate again, dispersing again, adding 0.06 part of dispersing agent lauryl alcohol ether phosphate, fully homogenizing and dispersing uniformly, centrifuging at high speed until the solid content is about 53%, and granulating to obtain the product
About 3mm, and then performing calcination according to the temperature of the temperature curve RT-100 ℃,30min,100-300 ℃,60min,300-450 ℃,60min and 450 ℃ for 60min to obtain a spherical composite catalyst;
synthesis of 2,2' -bipyridine: 30g of the composite catalyst is added on a fixed bed, the nitrogen flow rate is 120ml/min, the pyridine feeding flow rate is 0.5ml/min, the reaction temperature is 160 ℃,2' -bipyridine is obtained through post-treatment, the conversion rate of the pyridine can reach 9.2% through calculation, and the crude product is recrystallized to obtain white solid 2, 2-bipyridine, wherein the purity reaches 99.4%.
Example 5:
synthesis of composite catalyst: adding about 25% of the mixture with a size of Kong Zhanbi, 40% of mesopores, 32% of micropores and a specific surface area of about 320m into a homogenizer 2 1 part of per g carrier porous active carbon, adding 1.4 parts of ethanol, dispersing uniformly, adding 0.12 part of active component nickel dichloride hexahydrate again, dispersing again, adding 0.06 part of dispersing agent lauryl alcohol ether phosphate, fully homogenizing and dispersing until uniform, centrifuging at high speed until the solid content is about 53%, and granulating to obtain the product
About 3mm, and then performing calcination according to the temperature of the temperature curve RT-100 ℃,30min,100-300 ℃,60min,300-450 ℃,60min and 450 ℃ for 60min to obtain a spherical composite catalyst;
synthesis of 2,2' -bipyridine: 30g of the composite catalyst is added on a fixed bed, the nitrogen flow rate is 120ml/min, the pyridine feeding flow rate is 0.5ml/min, the reaction temperature is 160 ℃,2' -bipyridine is obtained through post-treatment, the conversion rate of the pyridine can reach 9.5% through calculation, and the crude product is recrystallized to obtain white solid 2, 2-bipyridine, wherein the purity reaches 99.6%.
The preferred embodiment of the invention shows that when the method of the invention uses the composite catalyst to prepare the 2, 2-bipyridine, the operation is simple, the reaction condition is mild, the single conversion rate of the pyridine is high, the conversion rate of the pyridine is further improved, and the method is favorable for industrial production.
Fig. 2-5 illustrate that the porous carbon parameters related in the invention can increase the distribution of active component nickel in the composite catalyst in the porous carbon, which is more beneficial to the contact of the composite catalyst and pyridine, improves the catalytic efficiency, and further improves the reaction efficiency of pyridine to obtain 2, 2-bipyridine.
The invention also provides a preparation method of the composite catalyst, which takes nickel compound as a catalytic active component, selects porous carbon with the mass content of Kong Zhanbi% -30%, the mesoporous ratio of 20% -50% and the micropore ratio of 10% -35% as a carrier, takes organic alcohol as a solvent, takes the mass content of the nickel compound as 1% -30% of the mass of the porous carbon, the mass ratio of the organic alcohol to the porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; the temperature is kept at 450 ℃ for 60min.
Based on the same conception as the method embodiment of the present invention, the specific content can be referred to the description of the method embodiment of the present invention for synthesizing 2,2' -bipyridine by using the composite catalyst, and the description is omitted here.
The preparation method of the composite catalyst adopts a high-efficiency homogenization method to take porous carbon with a certain proportion of holes as a carrier, takes the participation of a solvent to load active nickel, and carries out centrifugation and granulation on the homogenate to prepare the composite catalyst microsphere, so that the microsphere is calcined at a certain temperature to obtain the finished product composite catalyst for better solidifying the active nickel, thereby further improving the pyridine conversion rate, having low-cost and easily-obtained raw materials, effectively reducing the preparation cost of the composite catalyst, having toxicity resistance and being suitable for repeated use.
The invention also provides a composite catalyst, which is prepared by the preparation method of the composite catalyst. Based on the same conception as the preparation method of the composite catalyst, the specific content can be referred to the description in the embodiment of the method for synthesizing 2,2' -bipyridine by the composite catalyst, and the description is omitted here.
The composite catalyst provided by the invention takes porous carbon with a certain hole proportion as a carrier, active nickel is loaded under the participation of a solvent, and the composite catalyst microsphere is prepared by granulating after homogenate is centrifuged, so that the active nickel is better solidified, and the microsphere is calcined under a certain temperature curve, thereby further improving the pyridine conversion rate, being low in cost and easy to obtain raw materials, effectively reducing the preparation cost of the composite catalyst, having toxicity resistance and being suitable for repeated use.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. A method for synthesizing 2,2' -bipyridine by using a composite catalyst is characterized in that the composite catalyst is prepared by taking a nickel compound as a catalytic active component, selecting porous carbon with a large Kong Zhanbi-30%, a mesoporous content of 20-50% and a micropore content of 10-35% as a carrier, taking organic alcohol as a solvent, wherein the mass content of the nickel compound is 1-30% of the mass of the porous carbon, the mass ratio of the organic alcohol to the porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; preserving heat at 450 ℃ for 60min;
synthesis of 2,2' -bipyridine: pyridine enters a fixed bed layer of the composite catalyst microsphere under nitrogen purging to carry out coupling reaction to obtain a crude product, and 2,2' -bipyridine is obtained through purification.
2. The method for synthesizing 2,2' -bipyridine by using the composite catalyst according to claim 1, wherein the nickel compound comprises one or more of nickel nitrate, nickel dichloride hexahydrate and nickel sulfate.
3. The method for synthesizing 2,2' -bipyridine by using the composite catalyst according to claim 1, wherein porous carbon with a size of Kong Zhanbi% -25%, a size of Kong Zhanbi% -45% and a micropore ratio of 15% -25% is selected as a carrier.
4. The method for synthesizing 2,2' -bipyridine by using the composite catalyst according to claim 1, wherein porous carbon with specific surface area BET of 100-1000m2/g is selected as a carrier.
5. The method for synthesizing 2,2' -bipyridine by using the composite catalyst according to claim 1, wherein the dispersing agent is a zwitterionic surfactant and comprises one or more of alcohol ether phosphate, betaine type amphoteric surfactant and potassium laureth phosphate.
6. The method for synthesizing 2,2' -bipyridine by using the composite catalyst according to claim 1, wherein pyridine with a feeding flow rate of 0.02-0.4ml/min enters a fixed bed layer of the composite catalyst microsphere for coupling reaction under nitrogen purging with a flow rate of 60-200ml/min at a reaction temperature of 120-200 ℃.
7. A preparation method of a composite catalyst is characterized in that a nickel compound is used as a catalytic active component, porous carbon with a mass ratio of Kong Zhanbi% -30%, a mesoporous ratio of 20% -50% and a micropore ratio of 10% -35% is selected as a carrier, organic alcohol is used as a solvent, the mass content of the nickel compound is 1% -30% of the mass of the porous carbon, the mass ratio of the organic alcohol to the porous carbon is (1.5-2) (1-1.1),
preparing homogenate of the composite catalyst by using a homogenate method, wherein the solid content of the homogenate is 40% -65%, adding a dispersing agent accounting for 1% -10% of the mass of porous carbon into the homogenate for centrifugation and granulation to obtain composite catalyst microspheres, and calcining the composite catalyst microspheres according to a temperature curve to obtain the composite catalyst, wherein the temperature curve is RT-100 ℃ for 30min;100-300 ℃ for 60min;300-450 ℃ for 60min; the temperature is kept at 450 ℃ for 60min.
8. A composite catalyst prepared by a process for preparing a composite catalyst according to claim 7.
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