CH712355A2 - Synthesis of 2, 2'-bipyridyl using a supported bimetal nanoparticle catalyst. - Google Patents

Abstract

The present invention discloses the synthesis process of 2,2'-bipyridyl using a supported bimetallic nanoparticle catalyst, characterized by: by means of a supported bimetallic nanoparticle catalyst M 1 -M 2 @Al 2 O 3, pyridine becomes 2 by direct coupling , 2'-bipyridyl synthesized. With supported bimetal nanoparticle catalyst M 1 -M 2 @Al 2 O 3 Al 2 O 3 serves as a carrier and active ingredients are two different metals M 1 and M 2. M 1 and M 2 are each independently selected from noble metals Pd, Pt, Ru, Au, Ag, Rh or non-noble metals Ni, Cu, Fe, Zn, Co. This invention uses supported bimetallic nanoparticle catalyst in direct coupling synthesis of 2, 2'-bipyridyl from pyridine. The production efficiency is high, the production corresponds to the principles of the atom economy in chemical industry and no environmental pollution arises. This is a green production technology for the production of chemical intermediates.

Description

Description In the Technical Field [0001] This invention is a 2, 2'-bipyridyl synthetic method. This refers to the direct coupling of 2, 2'-bipyridyl using a bimetallic nanoparticle catalyst.

Background Art 2,2'-bipyridyl is one of the isomers of bipyridines. It can act as ligands, photosensitizers, indicators for the detection of metal ions, etc .; 2, 2 -Bipyridyl is also an important intermediate in the production of organic chemicals such. B. Key intermediate for the production of herbicide Diquatdi bromide. At present, the cheap herbicide paraquat is widespread. It is highly toxic and has no specific antidote to human and animal intoxication, so its use is limited. Diquatdibromide is considered the best alternative to paraquat. The production of its most important raw material 2,2'-bipyridyl determines its production costs. Therefore, the research and development of the green production technology of 2,2'-bipyridyl with high yields, low cost, high safety and low environmental impact has a good prospect and a high market value.

At home and abroad, many synthetic routes of bipyridyls have been reported, including in particular pyridine carbonyl cyclization compound synthesis, haloperidol-Ullmann coupling synthesis,

Raney nickel catalyst pyridinecarbonyl direct oxidation coupling synthesis and noble metal complexes catalysis etc.

For the first time, bipyridyl was cyclized from pyridinecarbonyl compounds. Beschke discovered in experiments that pyridinecarbonyl compound and α-ß-unsaturated carbonyl compound could be converted to 2, 2'-bipyridyl by using catalysts. At 440 ° C, 2-acetylpyridines, acrolein and ammonia were mixed in the molar ratio 1: 2: 6 and were converted to 2,2'-bipyridyl using catalyst. If 2-acetylpyridines is considered as the basis, the degree of conversion is up to 69%. Although this method has relatively high yields, the reaction temperature is too high. When the reaction is carried out in gas phase conditions, there are safety risks. In addition, this reaction and the catalytic efficiency is unstable. Finally, pyridinecarbonyl compounds are expensive and difficult to obtain. Therefore, this method has no value in industrial production.

Synthesized with the haloperidol-Ullmann coupling 2, 2'-bipyridyl has a relatively mature industrial application. The synthesis proceeds as follows: Pyridine as a raw material is converted by means of chlorine to chloropyridine and then coupled to 2, 2-bipyridyl. This technique and technology are relatively mature, but its synthesis route is relatively long and production efficiency relatively low. Hydrogen atom on the pyridine ring is first replaced by halogen atom and the halogen atom is subtracted while 2, 2'-bipyridyl is synthesized. In the ICI company, 2, 2'-bipyridyl was synthesized by Raney Nickel through Ullmann coupling. The reaction had to be heated at high pressure. Yield was pretty low. The Ullmann coupling process causes severe environmental pollution in the production process and production costs are relatively high, therefore, this method does not meet the principles of atom economy and requirements of modern green chemical production.

[0006] Bipyridyl direct coupling research using the Raney nickel catalyst and its reports have been around for a long time. By Gerald LGoe was in the 90s of the last century from pyridine using Raney nickel coupled directly to 2, 2-bipyridyl. The controlled reaction temperature was 200-400 ° C. After optimization of the conditions, the catalytic efficiency is 0.174 g of 2, 2'-bipyridyl per gram of Raney nickel per hour. If the reaction temperature were too high, Raney nickel would be slightly deactivated. If the temperature were too low, the yield would decrease. The direct coupling of bipyridyl with Raney nickel, however, has a short synthetic route and a simple production process, but the degree of conversion is low. In industrial production, Raney nickel catalysts are usually stored in water phase conditions and this reaction must be carried out under anhydrous conditions. In addition, the preparation and use of anhydrous Raney nickel catalyst are complicated and have some degree of safety risks.

In 2007, Takashi Kawashima et al. at JACS, the direct coupling of 2, 2-bipyridyl using Ru complex as a catalyst (Takashi Kawashima;

Toshiro Takao; Hiroharu Suzuki *. J. Am. 2,007,129 (36), 11006-11007.). After optimization of the conditions, the degree of conversion is 20%. But with this method, the synthetic route of the metal complex catalyst is complicated and expensive. Ru complex catalyst is considered to be a homogeneous catalyst that is difficult to recycle and difficult to reuse. Therefore, the industrial application value is limited.

In summary, there are a lot of synthetic routes of bipyridyl, but in industrial production bipyridyl is produced by the Uullman coupling. Due to the environmental pollution caused by this method, it does not comply with the modern concept of the green chemical industry. The design and preparation of the new catalysts, which allow pyridine to couple directly to 2, 2'-bipyridyl, has a very broad application potential.

CONTENT OF THE INVENTION The present invention overcomes the above shortcomings of existing technologies and offers a direct synthesis method of 2, 2'-bipyridyl using supported bimetallic nanoparticle catalyst M1-M2 @ Al203 to reduce production costs and operational safety to improve. It is suitable for industrial mass production.

The present invention discloses the synthesis method of 2, 2'-bipyridyl using supported bimetallic Na nopartikel catalyst, pyridine is coupled by supported bimetallic nanoparticle catalyst MrM2 @ Al 2 O 3 directly to 2, 2-bipyridyl. Reaction equation as follows (1):

In the equation, R 1, R 2, R 3, R 4 are each independently selected from H, methyl, ethyl, propyl, butyl, pentyl or hexyl; M1-M2 @ AI203 comes in high-pressure reactor and then pyridine. After replacing 02 with N2, the reactor is sealed. After 2 ~ 48 hours of reaction at the temperature 100 ~ 600 ° C, the heating is stopped, when the reactor temperature drops to room temperature, then reaction mixture can be obtained.

By filtering and precipitation of mixed reaction solution, solid is obtained. This is catalyst that can be reused. Fractionation of the reduced pressure filtrate gives unreacted pyridines and the desired product 2, 2'-bipyridyl.

Mass ratio of MrM2 @ AI203 and pyridine is 1: 1-10 000, the reaction temperature is 400 ° C, the reaction lasts 8 hours.

As described above, supported the carrier

Bimetal Nanoparticle Catalyst Mi-M2 @ Al203 is Al203 and any two metals are its active constituents. M, and M2 are each independently selected from noble metals Pd, Pt, Ru, Au, Ag, Rh or base metals Ni, Cu, Fe, Zn, Co. Preferably, the noble metal is Pd, Pt or Ru; the base metal Cu or Ni is preferred.

The support of the catalyst may be Al 2 O 3 of various crystal forms, e.g. α-ΑΙ203, β-ΑΙ203, γ-ΑΙ203 and bulky Al203. Of these, a-AI203, ß-AI203 and γ-ΑΙ203 have priority.

The molar ratio of above-described active ingredients M-, and M2 is 1: 0.01-100; the mass ratio of the above-described active ingredients is 5-60%, most preferably 30-50%; The corresponding active noble metal component of the catalyst Μί-Μ2 @ ΑΙ203 in this invention is converted from inorganic acid or organic acid salts with corresponding ions or organic metal compound, etc. as a precursor, e.g. RuCl3 3H20, RuO2, (NH4) 2RuCl6, [(C6H5) 3P] 3RuCl2, C15H2i06Ru, H2PtCle6H20, Pt-Cl4, PtCl3, PtCl2, [Pt (NH3) 4] (NO3) 2, (NH4) 2PtCl6, Pt (NO3 ) 2, (NH 4) 2 PtCl 4, C 10 H 14 O 4 Pt, Pd (NO 3) 2, Pd (OAc) 2, PdCl 2, Pd (OH) 2, PdSO 4 2H 2 O, Pd (NH 3) 2 Cl 2, Pd (NH 3) 4 Cl 2, Pd (C5H702) 2 , (NH4) 2PdCl4, Rh203, RhCl3-3H20, Rh (OAc) 3, Rh (NO3) 3 solution, Ru2 (SO4) 3 solution, (NH4) 3RhCl6; preferably acetate and chloride;

The corresponding non-precious metal active ingredient of the catalyst Μί-Μ2 @ ΑΙ203 in the invention is converted from inorganic acid or organic acid salts with corresponding ions or organic metal compound, etc. as a precursor, e.g. Cu (NO 3) 2-3H 2 O, CuCl 2 H 2 O, CuO, Cu 2 O, Cu (OAc) 2, Cu 2 (0H) 2CO 3, Ci0H14CuO 4, C 2 H 6 CuO 2, C 4 H 60 4 Co, CoCO 3, CoCl 2, CoSO 4 -7H 2 O, Co (OH) 2, Co (NO 3) 2, CoF2, CoCI2 (NH3) 4, C4H22Co04, CisH2CoO3, FeCl3, FeS, Fe2 (C204) 3-5H20, Fe (NO3) 3, Fe203, Fe304, Fe (C5H5) 2, trimethoxyiron, FeNH4 (S04) 212H20, Ci5H21Fe06, NiCI2, C4H6Ni04-4H20, Ni (OH) 2, NiSO4, Ni203, NiC03, Ni (OH) 3, Ni (NO3) 2, Ci0H14NiO4; prefers hydrochloride and nitrate.

The method of preparation of the supported bimetallic nanoparticle catalyst with the present invention may be nanoparticle-assisted synthesis or in situ assisted synthesis.

[0019] Steps of Nanoparticle-Assisted Synthesis: Alloyed nanoparticles MrM2 can be purchased or self-made. Depending on the nature and nature of the coating outside of alloyed nanoparticles, suitable solvents are selected (such as deionized water, alcohol, ether, preferably water and alcohol). Then, a solution of the alloyed nanoparticles with uniform and stable dispersion is compiled. After the desired proportion of appropriate amount of the above solution is taken. Thereafter, certain mass fraction of carriers is added and everything is mixed together and stirred constantly. At a suitable temperature, the solution is allowed to dry to remove solvent. After grinding, supported alloyed bimetallic nanoparticle catalyst is obtained by roasting, reduction, and high temperature annealing.

[0020] Steps of In-situ Assisted Synthesis of Catalyst: Precursor materials are weighed according to the ratio of active ingredients. Then they can be dissolved with water or suitable solvents and stirred. There are also carriers in this solution. Stir for a period of time until uniform viscous. Thereafter, at a suitable temperature, the solution is dried to remove solvent, after milling, supported bimetallic alloy nioparticle alloy catalyst can be obtained by roasting, reduction and high temperature annealing.

The advantageous effects are as follows: 1. With the invention, supported bimetallic nanoparticle catalyst is used in the preparation of 2, 2'-bipyridyl by direct coupling. The production efficiency is high, the production corresponds to the principles of the atom economy in chemical production, no environmental pollution arises, that is a green production technology with production of chemical intermediates.

2. With the synthesis method in the present invention can be recovered by fractionation with pressure reduction pyridines. The recovery rate is up to 90-98%, purity of the pyridines up to 98-99.5%, after distillation these pyridines can be reused directly. The recovered catalysts can be reused according to the specific circumstances directly or after simple drying. They still have high catalytic activity and product selectivity.

3. Dual active ingredients of the supported bimetallic nanoparticle catalyst in the present invention can effectively regulate the breaking of the C-H bond and the coupling of the C-C bond, thereby increasing the activity of the catalyst. As carriers, α-Al 2 O 3, β-Al 2 O 3 and γ-ΑΙ 203 have a larger area, and the interaction between them and each active ingredient is very strong, so that the active ingredients on the carrier remain stable. This is helpful for recovery and reuse.

Concrete Performance The following examples further describe the present invention. Example 1: Preparation and Catalytic Reaction of In-Situ Supported Metal Nanoparticle Catalyst Pd @ y-Al 2 O 3 (1) Preparation of Catalyst 2.00 g of PdCl 2 and 20 ml of deionized water are stirred in a container until complete dissolution; Add 4 g of AI203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, grind the milled particles in mixed atmosphere of N2 and H2 (N2 and H2) H2 in a volume ratio of 1: 1) at 450 ° C for 4 hours. This gives 5.03 g of supported metal-nanoparticle catalysts Pd @ γ-ΑΙ203. (2) Synthesis of 2, 2'-bipyridyl by a catalyst Add 4 g of catalysts and 40 g of pyridine in the high-pressure reactor in step (1), after replacing 02 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 34.8 g of pyridines (recovery rate is 95%, content fraction 98.5%) and 3.4 g of 2, 2'-bipyridyl (yield 8.5%).

Example 2: Preparation and catalytic reaction of the in-situ supported metal nanoparticle catalyst Cu @ yAl 2 O 3 (1) Preparation of the catalyst 5.34 g of CuCl 2 2H 2 O and 20 ml of deionized water are stirred in a container until completely dissolved ; 5g γ-ΑΙ203 are added to the above solution, then stirred for 4 hours until pasty, drying at 75 ° C for 12 hours, taking out the above solid and milling, the milled particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 450 ° C for 5 hours. This gives 6.89 g of supported metal nanoparticle catalysts Cu @ y-Al 2 O 3. (2) Synthesis of 2, 2-bipyridyl by a catalyst Add 4 g of catalysts charged in step (1) and 30 g of pyridines to the high pressure reactor, after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 10 hours of reaction, the heating is stopped. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 28.2 g of pyridines (recovery rate is 94%, salary 97.5%), No.2, 2'-bipyridyl.

Example 3: Preparation and Catalytic Reaction of the In Situ Supported Bimetallic Nanoparticle Catalyst Pd-Νί @ γ-ΑΙ203 (Pd and Ni in a molar ratio of 2: 1) (1) Preparation of Catalyst 2.34 g PdCl2, 1.92 g Νί (Ν03) 2 x 6Η20 and stir 30 ml of deionized water in a container until completely dissolved; Add 4 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 500 ° C for 5.5 hours. This gives 5.59 g of supported metal-nanoparticle catalysts Pd-Ni @ y-Al203. (2) Synthesis of 2, 2-bipyridyl by a catalyst Add 5 g of catalysts and 50 g of pyridines to the high pressure reactor in step (1), after replacing 02 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 22.0 g of pyridines (recovery rate is 92%, 95.7% salary) and 25.9g 2, 2-bipyridyl (yield 52%).

Example 4: Preparation and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Νί @ γ-ΑΙ203 (Pd and Ni in a 1: 1 molar ratio) (1) Preparation of Catalyst 2.34 g PdCl2,3.84 g of Ni (NO3) 2 6H20 and stir 30 ml of deionized water in a container until completely dissolved; Add 4 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 500 ° C for 5.5 hours. This gives 5.94 g of supported metal nanoparticle catalysts Pd-Ni @ Y-Al 2 O 3. (2) Synthesis of 2, 2-bipyridyl by a catalyst Add 5 g of the catalyst and 50 g of pyridine in the high-pressure reactor in step (1), after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 34.1g pyridines (recovery rate is 94%, content fraction 96.6%) and 13.5g 2, 2-bipyridyl (yield 27%).

Example 5: Preparation and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Cu @ y-Al 2 O 3 (Pd and Cu in a 3: 1 Molar Ratio) (1) Preparation of Catalyst 2.50 stir PdCl 2, 0.81 g of CuCl 2 2H 2 O and 30 ml of deionized water in a container until completely dissolved; Add 5 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the ground particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 480 ° C for 4.5 hours. This gives 6.58 g of supported metal nanoparticle catalysts Pd-Cu @ Y-AI203. (2) Synthesis of 2,2-bipyridyl by a catalyst. Add 5 g of catalyst added in step (1) and 40 g of pyridines to the high pressure reactor after replacing O2 with N2, sealing the reactor; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 9 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction sen sen 25.2g pyridines (recovery rate is 92%, content fraction 96.1%) and 12.1g 2, 2'-bipyridyl (yield 30%).

Example 6: Preparation and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Cu @ y-Al 2 O 3 (Pd and Cu in a 1: 1 Mole Ratio) (1) Preparation of Catalyst 2.50 g PdCl 2, 2.41 g of CuCl 2 2H 2 O and 30 ml of deionized water in a container until complete solution; Add 5 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the ground particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 480 ° C for 4.5 hours. This gives 7.12 g of supported metal-nanoparticle catalysts Pd-Cu @ y-Al203. (2) Synthesis of 2,2'-bipyridyl by a catalyst Add 5 g of the catalyst applied in step (1) and 40 g of pyridine to the high pressure reactor, after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 9 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 29.6g pyridines (recovery rate is 95%, content fraction 97.2%) and 8.4g 2, 2'-bipyridyl (yield 21%).

Example 7: Preparation and Catalytic Reaction of the In-Situ Supported Bimetal Nanoparticle Catalyst Ru-Cu @ v-Al 2 O 3 (Ru and Cu in a 1: 1 Mole Ratio) (1) Preparation of Catalyst 3.69 g RuCl2 3H20. Stir 3.05 g of CuCl 2 2H 2 O and 25 ml of deionized water in a container until completely dissolved; Add 4.5 g of γ-ΑΙ203 to the above solution, then stir for 4 hours to the pasty state, dry at 75 ° C for 12 hours, remove the above solid and grind, the ground particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 500 ° C for 4 hours. This gives 7.12 g of supported metal nanoparticle catalysts Ru-Cu @ y-Al203. (2) Synthesis of 2,2-bipyridyl by a catalyst. Add 5 g of catalyst and 50 g of pyridines in the high pressure reactor in step (1), after replacing 02 with N2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 10 hours of reaction, the heating is stopped. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 33.38 g of pyridine (recovery rate is 92%, content fraction 96.7%) and 13.4 g of 2, 2'-bipyridyl (yield 26.7%).

Example 8: Preparation and Catalytic Reaction of In-Situ Supported Bimetallic Nanoparticle Catalyst Pt-Cu @ y-Al 2 O 3 (Pt and Cu in 1.5: 1 molar ratio) (1) Preparation of Catalyst 2.66 g platinum. Stir 0.58 g of CuCl 2 2H 2 O and 20 ml of deionized water in a container until completely dissolved; Add 4 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 450 ° C for 5 hours. This gives 5.08 g of supported metal nanoparticle catalysts Pt-Cu @ Y-AI203. (2) Synthesis of 2, 2-bipyridyl by a catalyst Add 4.5 g of catalysts charged in step (1) and 40 g of pyridines to the high pressure reactor, after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction las sen 31.2 g of pyridine (recovery rate is 90%, 95.9% content content) and 4.68 g of 2, 2'-bipyridyl (yield 11.7%).

Example 9: Preparation and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Ru-Νί @ γ-ΑΙ203 (Ru and Ni in a molar ratio of 2: 1) (1) Preparation of Catalyst [0050] 3.07 g RuCI23H20. Stir 2.16 g Ni (N03) 2-6H20 and 25 ml deionized water in a container until completely dissolved; Add 5 g of γ-ΑΙ203 to the above solution, then stir for 4 hours until pasty, dry at 75 ° C for 12 hours, remove the above solid and grind, the ground particles are mixed in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 550 ° C for 5 hours. This gives 5.77 g of supported metal nanoparticle catalysts Ru-Ni @ y-Al 2 O 3. (2) Synthesis of 2,2'-bipyridyl by a catalyst [0051] Add 6 g of catalysts charged in step (1) and 35 g of pyridines to the high pressure reactor, after replacing O2 with N2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 26.2 g of pyridine (recovery rate is 91%, content fraction 97.4%) and 5.34 g of 2, 2'-bipyridyl (yield 15.3%).

Example 10: Preparation and Catalytic Reaction of the Nanoparticle-Supported Bimetal Nanoparticle Catalyst Pd-Ni @ y-Al 2 O 3 (3: 1): (1) Preparation of the Catalyst According to the literature [Feng, Li ; Chong, Hanbao; Li, Peng; Xiang, Ji; Fu, Fangyu; Yang, Sha; Yu, Hui; Sheng, Hongting; Zhu, Manzhou, Pd-Ni Alloy Nanoparticles as Effective Catalysts for Miyaura-Heck Coupling Reactions. Journal of Physical Chemistry C (2015), 119 (21), 11511-11515.] 5 g of alloyed Pd-Ni nanoparticles with a diameter of 10 nm (Pd and Ni in the molar ratio of 3: 1) and water are added to the dipersen solution (20 ml, the content of Pd is 30%) prepared. Add 4 g of γ-ΑΙ203 to the disperse solution and stir for 3 hours. The solvents of the mixed solution are removed in a vacuum drying oven at room temperature. The solid is ground. Finally, assisted alloyed bimetallic nanoparticle catalysts Pd-Ni @ y-Al203 are obtained at 550 ° C by roasting, 4 hours reduction and annealing. (2) Catalysis Synthesis of 2,2-bipyridyl Add 3 g of the catalysts prepared in step (1) and 30 g of pyridines to the high pressure reactor after replacing O2 with N2 to seal the reactor; Open the reactor, stir and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the gas generated in the reaction H2 is completely expelled. Filter and separate the removed reaction solution, recovering catalysts. These catalysts can be used directly. By fractionation of the filtrate with Druchverminde-tion to obtain 15.7 g of pyridines (recovery rate is 93%, content fraction 96.3%) and 12.9 g of 2, 2'-bipyridyls (yield 43.1%).

Example 11: Preparation and Catalytic Reaction of Nanoparticle-Supported Bimetallic Nanoparticle Catalyst R-Cu @ y-Al 2 O 3 (2: 1): (1) Preparation of Catalyst According to the literature [Lim, Taeho ; Kim, Ok-hee; Sung, Yung-eun; Kim, Hyun-Jong; Lee, Ho-Nyun; Cho, Yong-hun; Kwon, Oh Joong., Preparation of onion-like Pt-terminated Pt-Cu bimetallic nano-sized electrocatalysts for oxygen reduction reaction in fuel cells. Joumalof Power Sources (2016), 316, 124-131.] Are added 5 g of alloyed Pt-Cu Nanoparticles with diameter of 6 nm (Pd and Cu in the molar ratio of 3: 1) and water to the dipersen solution (20 ml, the content of Pt is 35%) prepared. Add 4 g of γ-ΑΙ203 to the disperse solution and stir for 3 hours. The solvents of the mixed solution are removed in a vacuum drying oven at room temperature. The solid is ground. Finally, supported bimetallic nanoparticle catalysts Pt-Cu @ v-Al203 are obtained at 400 ° C by roasting, 5-hour reduction and annealing. (2) Catalysis Synthesis of 2,2-bipyridyl Add 3 g of the catalysts prepared in step (1) and 40 g of pyridines to the high pressure reactor after replacing O 2 with N 2 to seal the reactor; Open the reactor, stir and heat until the reactor temperature reaches 400 ° C. After 10 hours of reaction, the heating is stopped. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the gas generated in the reaction H2 is completely expelled. Filter and separate the removed reaction solution, recovering catalysts. These catalysts can be used directly. By fractionation of the filtrate with Druchverminde-tion to obtain 30.2 g of pyridines (recovery rate is 94%, content fraction 95.9%) and 7.24 g of 2, 2'-bipyridyls (yield 18.1%).

EXAMPLE 12 Preparation and Catalytic Reaction of the Nanoparticle-Supported Bimetallic Nanoparticle Catalyst Pt-Pd @ Y-Al 2 O 3 (Pt and Pd in a Molar Ratio of 1: 1): (1) Preparation of the Catalyst [0059] 2.66 g of platinum. 0.91 g of PdCl 2 and 20 ml of deionized water in a container are stirred until complete solution: 5 g of y-Al 2 O 3 are added to the above solution, then stirred for 4 hours until pasty, drying at 75 ° C. for 12 hours, the above solid remove and grind the ground particles are activated in a mixed atmosphere of N2 and H2 (N2 and H2 in a volume ratio of 1: 1) at 380 ° C for 3.5 hours. This gives 6.41 g of supported metal nanoparticle catalysts Pt-Pd @ Y-Al 2 O 3. (2) Synthesis of 2, 2-bipyridyl by a catalyst Add 5 g of catalysts charged in step (1) and 40 g of pyridines to the high pressure reactor, after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 30.1 g of pyridines (recovery rate is 94%, content fraction 93.7%) and 7.32 g of 2, 2'-bipyridyl (yield 18.3%).

EXAMPLE 13 Preparation and Catalytic Reaction of the Nanoparticle-Supported Bimetallic Nanoparticle Catalyst Pt-Pd @ y-Al 2 O 3 (Pt and Pd in a 2: 1 Molar Ratio): (1) Preparation of the Catalyst [0062] 5.32 g of platinum. Stir 0.91 g of PdCl 2 and 25 ml of deionized water in a container until completely dissolved; Add 5 g of y-Al 2 O 3 in the above solution, then stir for 4 hours to the pasty state, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N 2 and H 2 (N 2 and H2 in a volume ratio of 1: 1) at 380 ° C for 3.5 hours. This gives 7.31 g of supported metal-nanoparticle catalysts R-Pd @ y-Al203. (2) Synthesis of 2, 2'-bipyridyl by a catalyst Add 5 g of catalyst and 40 g of pyridine in the high-pressure reactor in step (1), after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 28.3 g of pyridines (recovery rate is 93%, 95.9% content content) and 9.04 g of 2, 2-bipyridyl (yield 22.6%).

EXAMPLE 14 Preparation and Catalytic Reaction of the Nanoparticle-Supported Bimetal Nanoparticle Catalyst Cu-Ni @ y-Al 2 O 3 (Cu and Ni in a Molar Ratio of 1: 1): (1) Preparation of the Catalyst [0065] 3.21 g CuCI23H20 5.45 g Ni (N03) 2-6H20 and 25 ml deionized water in a container until complete solution; Add 4 g of Y-Al 2 O 3 to the above solution, then stir for 4 hours to the pasty state, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N 2 and H 2 (N 2 and H2 in a volume ratio of 1: 1) at 600 ° C for 7 hours. This gives 6.18 g of supported metal nanoparticle catalysts Cu-Ni @ y-Al203.

(2) Synthesis of 2, 2'-bipyridyl by a catalyst To add 3 g of the catalysts spread in step (1) and 60 g of pyridines to the high pressure reactor after replacing O 2 with N 2, becomes the reactor sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 52.7 g of pyridine (recovery rate is 93%, 95.0% salary) and 3.48g 2, 2'-bipyridyl (yield 5.8%).

Example 15: Preparation and Catalytic Reaction of the Nanoparticle-Supported Bimetallic Nanoparticle Catalyst Pd-Ni @ a-Al 2 O 3 (Pd and Ni in a 2: 1 Molar Ratio): (1) Preparation of Catalyst [0069] 2.34 g of PdCl 2, 1.92 g of Ν (Ν03) 2 x 6Η20 and 30 ml of deionized water in a container until complete solution; Add 4 g of y-Al 2 O 3 to the above solution, then stir for 4 hours to the pasty state, dry at 75 ° C for 12 hours, remove the above solid and grind, the milled particles are mixed in a mixed atmosphere of N 2 and H 2 (N 2 and H2 in a volume ratio of 1: 1) at 500 ° C for 5.5 hours. This gives 6.59 g of supported metal-nanoparticle catalysts Pd-Ni @ a-Al203. (2) synthesis of 2,2'-bipyridyl by a catalyst add 4 g of catalysts and 40 g of pyridines in the high pressure reactor in step (1), after replacing O 2 with N 2, the reactor is sealed; Open the reactor and heat until the reactor temperature reaches 400 ° C. After 8 hours of reaction, heating stops. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated gas H2 is totally expelled. From the high pressure reactor, the reaction solution is taken out, then filtered and separated. Catalysts are thereby obtained, which can be reused directly. By fractionation of the filtrate with pressure reduction can be 24.3 g of pyridines (recovery rate is 90%, content fraction 94.8%) and 12.4g 2, 2-bipyridyl (yield 531.0%).

EXAMPLE 16 Production and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Ni @ y-Al 2 O 3 (Pd-Ni Molar Ratio 2: 1): (1) Preparation of the Catalyst as Example 3 (FIG. 2) Catalyst 4-methyl pyridine and synthesize 4,4'-dimethyl-2,2'-bipyridyl 5.0 g of catalysts prepared in step (1) and 50 g of 4-methylpyridine are added to the high pressure reactor , After replacing 02 with N2, the reactor is sealed. Open the reactor, stir and heat until the reactor temperature reaches 400 ° C; after 11 hours of reaction with heating stop when the reactor temperature drops to room temperature, the valve of the high-pressure reactor can be opened. The gas generated in the reaction H2 is completely expelled. The mixed reaction solution is taken out of the high pressure reactor, then filtered and separated. As a result, catalysts are recovered, which can be used directly again. When fractionating the filtrate by pressure reduction 31.1 g of 4-methyl-pyridines (recovery rate 90%, content 96.1%) and 14.8 g of 4,4'-dimethyl-2, 2'-bipyridyls (recovery rate 29.6%) to win back.

Example 17: 2, 2-Bipyridyl synthesize from recovered pyridines (1) Preparation of the catalyst as Example 3; (2) Catalysis Synthesis of 2,2-bipyridyl 2.5 g of catalysts prepared in step (1) and 20 g of recovered pyridines (content> 98.0%) are added to the high pressure reactor. After replacing 02 with N2, the reactor is sealed. Then the high pressure reactor is opened and heated until the reactor temperature reaches 400 ° C; after 8 hours of reaction, the heating is stopped. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated H2 is completely expelled. Finally, the reaction solution is taken out of the reactor, filtered and separated. Catalysts are recovered, which can be used directly again. By fractionation of the filtrate with pressure reduction 9.05 g of pyridine (recovery rate 91%, content 94.6%) and 10.02 g of 2, 2'-bipyridyl (recovery rate 50.1%) to recover.

Example 18: Research on properties of the recovered catalyst

Claims (5)

(1) Catalysts are the catalysts recovered in Example 3 (2) Synthesis of 2, 2'-bipyridyl 30 g of pyridines and 3 g of catalysts recovered in Example 3 are added to the high-pressure reactor. After replacing 02 with N2, the reactor is sealed. Then the high pressure reactor is opened and heated until the reactor temperature reaches 400 ° C; after 8 hours of reaction, the heating is stopped. When the reactor temperature drops to room temperature, the valve of the reactor can be opened. As a result, the generated H2 is completely expelled. Finally, the reaction solution is taken out of the reactor, filtered and separated. As a result, catalysts are recovered, which can be used directly again. By fractionation of the filtrate with pressure reduction to obtain 13.9 g of pyridines (recovery rate 92%, salary 95.8%) and 14.55 g 2, 2'-bipyridyls (recovery rate 48.2%). Claims 1. The synthesis process of 2,2'-bipyridyl with the aid of the supported bimetallic nanoparticle catalyst is characterized in that pyridine is converted to 2,2'-bipyridyl by supported bimetallic nanoparticle catalyst M- | -M2 @ Al203 coupled. Reaction equation as follows (1): In the equation, R 1, R 2, R 3, R 4 are each independently selected from H, methyl, ethyl, propyl, butyl, pentyl or hexyl; Said supported bimetallic nanoparticle catalyst MrM2 @ Al203 is based on Al 2 O 3 as carrier and its active ingredients are two arbitrarily different metals M 1 and M 2. M- and M2 are each independently selected from noble metals Pd, Pt, Ru, Au, Ag, Rh or non-noble metals Ni, Cu, Fe, Zn, Co. 2. The method of synthesis indicated in claim 1 is characterized in that it is carried out as follows: MrM2 @ Al203 is in high-pressure reactor and then pyridine. After replacing 02 with N2, the reactor is sealed. After 2 ~ 48 hours reaction at the temperature 100-600 ° C, the heating is stopped, when the reactor temperature drops to room temperature, then reaction mixture can be obtained. By filtering and precipitating mixed reaction solution, solid is obtained. This is catalyst that can be reused. Fractionation of the reduced pressure filtrate gives unreacted pyridines and the desired product 2,2-bipyridyl. 3. The synthesis method given in claim 2 is characterized by: Mass ratio of Mr M2 @ Al 2 O 3 and pyridine is 1: 1-10000. 4. 4. The synthesis method given in claim 3 is characterized by: mass ratio of M ·, -M2 @ Al203 and pyridine is 1: 4-50. 5. The specified in claim 2 synthesis method is characterized by: the reaction temperature is 4000 ° C, the reaction lasts 8 hours.