BE1023807B1 - Synthesis of 2, 2'-bipyridyl using supported bimetal nanoparticle catalyst - Google Patents

Abstract

The present invention discloses the synthesis method of 2, 2'-bipyridyl using supported bimetallic nanoparticle catalyst, characterized by: assisted bimetallic nanoparticle catalyst M1-M2 @ Al2O3 pyridine is synthesized by direct coupling to 2, 2'-bipyridyl. With supported bimetallic nanoparticle catalyst M1-M2 @ Al2O3, Al2O3 acts as a carrier and active components are two different metals M1 and M2. M1 and M2 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

Synthesis of 2, 2'-bipyridyl using supported bimetal nanoparticle catalyst

In the technical area

This invention is a synthesis process of 2,2'-bipyridyl. This refers to the direct coupling of 2, 2'-bipyridyl using a

Bimetallic nanoparticle catalyst.

Technical Background 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 Diquatdibromide. 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 pathways of bipyridyls have been reported, including, in particular, pyridinecarbonyl compound cyclization synthesis,

Haloperidol Ullmann coupling synthesis,

Raney nickel catalyst-pyridinecarbonyl direct oxidation coupling synthesis and

Noble metal complex catalysis etc.

For the first time, bipyridyl was cyclized from pyridinecarbonyl compounds. Beschke discovered in experiments that pyridinecarbonyl compounds and a-ß-unsaturated carbonyl compounds could be converted to 2, 2'-bipyridyl catalysts at 440 ° C, 2-acetylpyridines, acrolein, and ammonia in a molar ratio of 1: 2: 6 were converted to 2, 2'-bipyridyl with the help of catalyst. If 2-acetylpyridines are 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.

2, 2'-bipyridyl synthesized by the haloperidol-Ullmann coupling has a relatively mature industrial application. The synthesis proceeds as follows: pyridine as a raw material is converted to chloropyridine with the aid of chlorine 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.

The research on bipyridyl direct coupling using the Raney nickel catalyst and its reports have been around for a long time. In the 1990s, Gerald L. Gooe coupled pyridine directly to 2, 2'-bipyridyl using Raney nickel. 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. Although the direct coupling of bipyridyl with Raney nickel has a short synthesis route and a simple production process, 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 hazards.

In 2007, Takashi Kawashima et al. in JACS, the direct coupling of 2,2'-bipyridyl using Ru complex as catalyst (Takashi Kawashima, Toshiro Takao, Hiroharu Suzuki *, J. Am. Chem. Soc., 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 perspective.

Content of the invention

The present invention avoids the shortcomings of existing technologies described above and offers a direct synthesis method of 2, 2'-bipyridyl with the aid of supported bimetallic nanoparticle catalyst Mi-M2 @ Al2C> 3 to reduce production costs and improve operational safety. It is suitable for industrial mass production.

The present invention discloses the synthesis method of 2, 2'-bipyridyl using supported bimetal nanoparticle catalyst, pyridine is coupled by supported bimetallic nanoparticle catalyst Μι-Μ2 @ Al2O3 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;

Mi-M2 @ AI2O3 comes in high-pressure reactor and then pyridine. After replacing O2 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 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.

Mass ratio of Μι-Μ2 @ Αΐ2θ3 and pyridine is 1 1-10000, the

Reaction temperature is 400 ° C, the reaction lasts 8 hours.

As outlined above, the support supported bimetallic nanoparticle catalyst Mi-M2 @ Al2O3 is Al2O3 and any two metals are its active constituents. Here, Mi 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. a-Al203, β-Al2O3, γ-Α1203 and unsubstituted Al2O3. Of these, α-Α1203, β-AI2O3 and γ-Α1203 have priority.

The molar ratio of the above-described active ingredients Mi 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 Μι-Μ2 @ Αΐ2θ3 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) 2RuC16, [(C0HsjsPjsRuCb, C15H21O6RU, H2PtCl6'6H20, PtCl4, PtCl3, PtCl2, [Pt (NH3) 4] (NO3) 2, (Ml ^ tCle, Pt (NO3) 2, (NH4) 2PtCl4, Ci0Hi4O4Pt, Pd (NO3) 2, Pd (OAc) 2, PdCl2, Pd (OH) 2, PdSO4-2H20, Pd (NH3) 2Cl2, Pd (NH3) 4Cl2, Pd (C5H702) 2, ( NH4) 2PdCl4, Rh203, RI1Cl3 3H20, Rh (OAc) 3, Rh (NO3) 3 solution, Ru2 (SO4) 3 solution, (NH4) 3RhCl6, preferably acetate and chloride;

The corresponding active non-noble metal component of the catalyst Μι-Μ2 @ Αΐ2θ3 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, CuC 12 2H 2 O, CuO, Cu 2 O, Cu (OAc) 2, Cu 2 (0H) 2CO 3, CioHi 4 CuO 4, C 2 H 6 CuO 2, C 4 H 604 Co, COCO 3, CoCl 2, CoSO 4 7H 2 O, Co (OH) 2, Co (NO 3) 2 , CoF2, CoC12 (NH3) 4, Ci4H22Co04, Ci5H21Co06, FeCl3, FeS, Fe2 (C204) 3 5H20, Fe (NO3) 3, Fe203, Fe304, Fe (C5H5) 2, trimethoxyiron, FeNH4 (SO4) 2 12H20, Ci5H2iFe06 , NiCl2, C4H6Ni04 4H20, Ni (OH) 2, NiSO4, Ni203, N1CO3, Ni (OH) 3, Ni (NO3) 2, CioHi4Ni04; 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.

Nanoparticle-Assisted Synthesis Steps: Alloy Nanoparticles Mi-M2 can be purchased or self-fabricated. 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 put together. 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.

Catalyst In Situ Supported Synthesis Steps: 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. The synthesis method in the present invention can recover pyridine by fractional reduction. 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-Α1203 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 execution

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 Mix 2.00 g of PdCl 2 and 20 ml of deionized water in a container until complete dissolution; Add 4 g of γ-¹1203 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 450 ° C for 4 hours. This gives 5.03 g of supported metal nanoparticle catalysts Pd @ γ-Α1203. (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 discharged. 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 C> 3 (1) Preparation of Catalyst 5.34 g of CuC 12-2H 2 O and stir 20 ml of deionized water in a container until complete dissolution; 5g γ-Α1203 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 volumetric ratio of 1: 1) at 450 ° C for 5 hours. This gives 6.89 g of supported metal nanoparticle catalysts Cu @ y-Al2C> 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 O 2 is replaced by 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 discharged. 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 In Situ Supported

Bimetallic nanoparticle catalyst Pd-Ni @ y-Al 2 O 3 (Pd and Ni in a molar ratio of 2: 1) (l) Preparation of Catalyst 2.34g PdCl 2. Stir 192g Ni (N03) 2 6H20 and 30ml deionized water in a container until complete dissolution; Add 4 g of γ-¹1203 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 5.5 hours. This gives 5.59 g of supported metal-nanoparticle catalysts Pd-Ni @ y-Al203. (2) synthesis of 2, 2'-bipyridyl by adding a catalyst 5g in step (1) and 50 g of pyridines in the high-pressure reactor after 02 is replaced by 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 discharged. 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 pyridine (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-Ni @ y-Al2C> 3 (Pd and Ni in a 1: 1 molar ratio) (1) Preparation of Catalyst 2.34g PdCh. Stir 3.84g Ni (N03) 2-6H20 and 30ml deionized water in a container until completely dissolved; Add 4 g of YA ^ Os 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 5.5 hours. This gives 5.94 g of supported metal-nanoparticle catalysts Pd-Ni @ Y-Al2C> 3. (2) synthesis of 2,2'-bipyridyl by adding a catalyst 5g in step (1) and 50 g of pyridines to the high pressure reactor after O2 is replaced by 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 discharged. 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 In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Cu @ Y-Al 2 O 3 (Pd and Cu in 3: 1 molar ratio) (1) Preparation of Catalyst 2.50 g PdCh. Stir 0.81 g of CuCl 2H 2 O and 30 ml of deionized water in a container until completely dissolved; Add 5 g of γ-¹1203 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 480 ° C for 4.5 hours. This gives 6.58 g of supported metal-nanoparticle catalysts Pd-Cu @ Y-Al2C> 3. (2) synthesis of 2, 2'-bipyridyl by adding a catalyst 5g in step (1) and 40 g of pyridines to the high pressure reactor after O2 is replaced by N2, 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 discharged. 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 25.2g pyridines (recovery rate is 92%, salary 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-CufSy-AkCk (Pd and Cu in a 1: 1 molar ratio) (l) Preparation of Catalyst 2.50g PdCk, 2.41g CuCk 2H2O and Stir 30 ml of deionized water in a container until completely dissolved; Add 5 g of γ-AkCh 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 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-Ak03. (2) synthesis of 2, 2'-bipyridyl by adding a catalyst 5g in step (1) and 40 g of pyridines to the high pressure reactor after O2 is replaced by N2, 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 discharged. 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 Bimetallic Nanoparticle Catalyst Ru-Cui ^ y-AkCk (Ru and Cu in a 1: 1 molar ratio) (l) Preparation of Catalyst 3.69 g RuC12 3H20. Stir 3.05 g CuCl2'2H20 and 25 ml deionized water in a container until completely dissolved; Add 4.5 g of γ-Αΐ2θ3 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 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 adding a catalyst 5g in step (1) and 50 g of pyridines in the high-pressure reactor after 02 is replaced by 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 discharged. 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 the In Situ Supported Bimetallic Nanoparticle Catalyst Pt-Cu @ y-Al 2 O 3 (Pt and Cu in a 1.5: 1 molar ratio) (l) Preparation of the catalyst 2.66 g of platinum 0.058 g of CuCl22H 2 O and stir 20 ml of deionized water in a container until completely dissolved; Add 4 g of γ-¹1203 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 volumetric ratio of 1: 1) at 450 ° C for 5 hours. This gives 5.08 g of supported metal nanoparticle catalysts Ρί-Οι @ γ-Α12θ3. (2) Synthesis of 2, 2'-bipyridyl by a catalyst 4.5g in step (1) applied catalysts and 40 g of pyridines in the

Add high-pressure reactor after O2 is replaced by 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 discharged. 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 31.2 g of pyridines (recovery rate is 90%, content fraction 95.9%) and 4.68 g of 2, 2'-bipyridyl (yield 11.7%).

Example 9: Preparation and Catalytic Reaction of In Situ Supported

Bimetallic nanoparticle catalyst Ru-Ni ^ iy-AfCL (Ru and Ni in a molar ratio of 2: 1) (l) Preparation of Catalyst 3.07 g of RuCb 3H 2 O, 2.16 g of Ni (NO 3) 2 .6H 2 O and 25 ml of deionized water in one Stir containers until complete dissolution; Add 5 g of γ-Αΐ2θ3 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 volumetric ratio of 1: 1) at 550 ° C for 5 hours. This gives you 5.77 g supported

Metal nanoparticle catalysts Ru-Ni @ y-Al2C> 3. (2) synthesis of 2, 2'-bipyridyl by adding a catalyst 6 g in step (1) and 35 g of pyridines in the high-pressure reactor after O2 is replaced by 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 discharged. 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 Nanoparticle-Supported

Bimetallic Nanoparticle Catalyst Pd-Ni @ γ-Αΐ2θ3 (3: 1): (1) Preparation of 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-Αΐ2θ3 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 3 g of prepared catalysts in step (1) and 30 g of pyridines are added to the high pressure reactor after O 2 is replaced by N 2, the reactor is to be sealed; 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 H2 generated in the reaction is completely discharged. Filter and separate the removed reaction solution, recovering catalysts. These catalysts can be used directly. By fractionation of the filtrate with Druchverminderung obtained 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 Pt-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 nanoscale electrocatalysts for oxygen production reaction in fuel cells. Joumalof Power Sources (2016), 316, 124-131. ] are prepared 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%). Add 4 g of γ-Αΐ2θ3 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 Pt-Cu @ Y-Al2C> 3 are obtained at 400 ° C by roasting, 5-hour reduction and annealing. (2) catalyzed synthesis of 2, 2'-bipyridyl 3 g of prepared catalysts in step (1) and 40 g of pyridines are added to the high pressure reactor after O 2 is replaced by N 2, the reactor is to be sealed; 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 H2 generated in the reaction is completely discharged. Filter and separate the removed reaction solution, recovering catalysts. These catalysts can be used directly. By fractionation of the filtrate with Druchverminderung obtained 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 Nanoparticle-Supported

Bimetallic Nanoparticle Catalyst Pt-Pd @ y-Al 2 O 3 (Pt and Pd in a 1: 1 molar ratio): (1) Preparation of Catalyst 2.66 g of platinum. Stir 0.91 g PdCl2 and 20 ml deionized water in a container until completely dissolved; Add 5 g of γ-¹1203 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 volumetric ratio of 1: 1) at 380 ° C for 3.5 hours. This gives 6.41 g of supported metal nanoparticle catalysts Pt-Pd @ y-Al2C> 3. (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 discharged. 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 Bimetal Nanoparticle Catalyst Pt-Pd @ y-Al 2 C> 3 (Pt and Pd in a 2: 1 molar ratio): (1) Preparation of Catalyst 5.32 g of platinum. Stir 0.91 g of PdCl2 and 25 ml of deionized water in a container until completely dissolved; Add 5 g of γ-¹1203 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) 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 Pt-Pd @ y-Al2C> 3. (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 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 discharged. 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%, content fraction 95.9%) and 9.04 g of 2, 2'-bipyridyl (yield 22.6%).

Example 14: Preparation and Catalytic Reaction of the Nanoparticle Supported Bimetallic Nanoparticle Catalyst Cu-NifSy-AfO ^ (Cu and Ni in a 1: 1 molar ratio): (1) Preparation of the catalyst 3.21 g CuCb 3H2CK 5.45 g Ni (NO3 ) Stir 2 6H20 and 25 ml deionized water in a container until completely dissolved; 4 g of yA ^ CE are added to the above solution, then stirred for 4 hours to the pasty state, dry at 75 ° C for 12 hours, take out 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 600 ° C for 7 hours. This gives 6.18 g of supported metal nanoparticle catalysts Cu-Ni @ γ-Al2O3. (2) synthesis of 2, 2'-bipyridyl by a catalyst add 3 g of catalyst added in step (1) and 60 g of pyridines to the high pressure reactor after O 2 is replaced by 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 discharged. 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 C> 3 Pd and Ni in a 2: 1 Molar Ratio): (1) Preparation of Catalyst 2.34 g PdCl 2> 1.92 g Stir Ni (N03) 2-6H20 and 30 ml of deionized water in a container until completely dissolved; Add 4 g of YA ^ Cb 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 volumetric 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 catalyst and 40 g of pyridine in the high pressure reactor in step (1), 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 discharged. 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: Preparation and Catalytic Reaction of the In-Situ Supported Bimetallic Nanoparticle Catalyst Pd-Ni @ y-Al 2 O 3 (Pd: Ni mole ratio is 2: 1): (1) Preparation of Catalyst as Example 3 (2) 4 -Catalyze methyl pyridine and synthesize 4, 4'-dimethyl-2,2'-bipyridyl. 5.0 g of catalysts prepared in step (1) and 50 g of 4-methyl-pyridines 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 H2 generated in the reaction is completely exhausted. 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 31.1g 4-methyl-pyridines (recovery rate 90%, content 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) production 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 O 2 is replaced by N 2, the reactor is sealed off. 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 (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 O2 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 (5)

claims 1. The synthesis of 2, 2'-bipyridyl using the supported bimetal nanoparticle catalyst is characterized by: Pyridine is coupled directly to 2,2'-bipyridyl through supported bimetallic nanoparticle catalyst Ml-M2 @ A1203. Reaction equation as follows (1): (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 bimetal nanoparticle catalyst Ml-M2 @ A1203 is based on A1203 as carrier and its active ingredients are any two metals Ml and M2. Ml 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 synthesis process specified in claim 1 is characterized in that it takes place as the following sections: Ml-M2 @ A1203 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 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 M1-M2 @ A1203 and pyridine is 1: 1-10000. 4. The synthesis method given in claim 3 is characterized by: Mass ratio of M1-M2 @ A1203 and pyridine is 1: 4-50. 5. The specified in claim 2 synthesis method is characterized by: the reaction temperature is 400 ° C, the reaction lasts 8 hours.