CN105859610A - Synthesis method of 2,2'-dipyridine by using supported bimetal nano catalyst - Google Patents

Synthesis method of 2,2'-dipyridine by using supported bimetal nano catalyst Download PDF

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CN105859610A
CN105859610A CN201610261790.8A CN201610261790A CN105859610A CN 105859610 A CN105859610 A CN 105859610A CN 201610261790 A CN201610261790 A CN 201610261790A CN 105859610 A CN105859610 A CN 105859610A
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catalyst
pyridine
bipyridyl
autoclave
reaction
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CN105859610B (en
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冯乙巳
王光宇
姜伟伟
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Hefei University of Technology
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Hefei University of Technology
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Priority to PCT/CN2016/086353 priority patent/WO2017181514A1/en
Priority to BE2016/5630A priority patent/BE1023807B1/en
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Abstract

The invention discloses a synthesis method of 2,2'-dipyridine by using a supported bimetal nano catalyst. The method is characterized in that the supported bimetal nano catalyst M1-M2@Al2O3 is utilized to catalyze the direct coupling reaction of pyridine so as to synthesize the 2,2'-dipyridine. The supported bimetal nano catalyst M1-M2@Al2O3 uses Al2O3 as a supporter and any two different metals M1 and M2 as active components, wherein M1 and M2 are respectively and independently selected from noble metals Pd, Pt, Ru, Au, Ag and Rh, or non-noble metals Ni, Cu, Fe, Zn and Co. By using the supported bimetal nano catalyst in direct coupling production of 2,2'-dipyridine from pyridine, the method has high production efficiency, conforms to the atom economy principle in chemical industry production, does not generate any pollutant which is harmful to the environment, and thus, is a green chemical-industry intermediate production technique.

Description

Use the synthetic method of 2,2 '-bipyridyl of load type double-metal nanocatalyst
One, technical field
The present invention relates to one 2, the synthetic method of 2 '-bipyridyl, be specifically related to load type double-metal nanocatalyst catalytic pyridine Directly coupling synthesis 2, the method for 2 '-bipyridyl.
Two, background technology
2,2 '-bipyridyl, can be as part, photosensitizer, the indicator of detection metal ion as one of the isomer of bipyridyl Deng；2, the important intermediate in 2 '-bipyridyl or organic chemical industry's production, such as the key intermediate produced as herbicide diquat dibromide. The existing cheap herbicides paraquat being widely used due to its hypertoxicity, because of after person poultry poisoning without specially good effect antidote so that it is should With being restricted.Diquat dibromide herbicide is as the best substitute kind of N,N'-dimethyl-.gamma..gamma.'-dipyridylium, and its primary raw material 2, the production of 2 '-bipyridyl determines Its production cost.Therefore, high yield, low cost, good and oligosaprobic 2,2 ' the bipyridyl greens productions of safety are researched and developed Technology, will have important application prospect and market value.
Report has multiple bipyridyl synthetic route both at home and abroad, mainly includes pyridine carbonyl based compound Cyclization method, haloperidid Ullmann coupling synthetic method, raney ni catalysis pyridine direct oxidation coupling synthetic method and the catalysis method etc. of precious metals complex.
Bipyridyl synthetic method the earliest is to prepare with pyridine carbonyl based compound cyclization.Beschke in experiments it is found that pyridine carbonyl Compound and alpha-beta-beta-unsaturated carbonyl compounds can be with Cyclization 2,2 '-bipyridyls under the effect of catalyst.Will at 440 DEG C Mol ratio is the 2-acetylpyridine of 1:2:6, acrylic aldehyde and ammonia mixing, produces 2 under catalyst action, 2 '-bipyridyl, On the basis of 2-acetylpyridine, conversion ratio is up to 69%.Although the method yield is higher, but reaction temperature is too high, instead Should carry out under gas phase condition, there is production safety hidden danger；This reaction stability and catalytic efficiency are unstable；Secondly pyridine carbonyl Compound is expensive, is relatively difficult to obtain, and therefore the method does not possess commercial production value.
Haloperidid Ullmann coupling synthesis 2,2 '-bipyridyl has had more ripe commercial Application.Its building-up process is: It is converted into chloro-pyridine, then coupling synthesis 2,2 '-bipyridyl for raw material by chloro with pyridine.The technology of the method and technique are Comparative maturity, but that route be synthesized is the longest for it, and production efficiency is relatively low；On pyridine ring, hydrogen atom is first former by halogen Son replaces, and synthesizes 2, is taken off by halogen atom during 2 '-bipyridyl again.ICI company once applied the Ullmann coupling of raney ni catalysis Synthesis 2,2 '-bipyridyl, under high pressure reacting by heating, but productivity is relatively low.Ullmann coupling method production process can cause very Big pollution, product cost is of a relatively high, and the production requirement with atom economy and Modern Green chemical industry does not meets.
Pyridine direct coupling synthesis bipyridyl research and report existing long period under anhydrous raney ni catalysis.Gerald L.Goe exists The nineties in last century once with raney ni catalysis pyridine direct coupling synthesis 2,2 '-bipyridyl, controlled reaction temperature and was 200-400 DEG C, After optimal conditions catalytic efficiency reach 0.174g 2,2 '-bipyridyl/g Raney's nickel/hour.Owing to reaction temperature is the highest, Raney's nickel is very Easily inactivation, but temperature too low-yield just declines.Although raney ni catalysis pyridine direct coupling synthesis bipyridyl synthetic route is short, Production process is simple, but reaction conversion ratio is low, and the Raney's nickel catalyst of industrial production is generally held in aqueous phase system, and The direct coupling reaction of its catalytic pyridine needs carrying out in anhydrous conditions, prepares and uses anhydrous Raney's nickel catalyst complex operation, There is certain security risk.
Takashi Kawashima in 2007 etc. report on JACS Ru complex-catalyzed pyridine direct coupling synthesis 2,2 '- Method (the Takashi Kawashima of bipyridyl；Toshiro Takao；Hiroharu Suzuki*.J.Am.Chem.Soc. 2007,129 (36), 11006-11007.), can reach 20% through condition optimizing conversion per pass.But metal combination in the method Thing catalyst complex synthetic route, expensive；Ru composition catalyst used is homogeneous catalyst, reclaims complexity, work Difficulty is reused big, so production application is worth limited in industry.
In sum, although bipyridyl has multiple synthetic route, but industrial still employing chloro-pyridine is by Uullman coupling Reaction produces, and the essential contaminative of the method does not meets Modern Green chemical industry theory.Design and prepare new catalyst, be catalyzed pyrrole Pyridine direct coupling synthesis 2,2 '-bipyridyl has the most wide application prospect.
Three, summary of the invention
The present invention is for avoiding the weak point existing for above-mentioned prior art, it is provided that a kind of with load type double-metal nanocatalyst M1-M2@Al2O3Efficient catalytic pyridine is directly synthesized 2, the method for 2 '-bipyridyl, it is intended to reduces production cost, improve operation peace Quan Xing, with applicable large-scale industrial production.
The present invention uses the 2 of load type double-metal nanocatalyst, the synthetic method of 2 '-bipyridyl, and its feature is: with support type Bimetal nano catalyst M1-M2@Al2O3For catalyst, catalytic pyridine direct coupling reaction synthesis 2,2 '-bipyridyl, reaction Shown in equation such as formula (1):
R in formula1、R2、R3、R4It is independently selected from H, methyl, ethyl, propyl group, butyl, amyl group or hexyl；
Above-mentioned synthetic method is to carry out as follows:
By M1-M2@Al2O3Join in autoclave, and add pyridine, use N2O in displacement autoclave2After, Sealed reactor；It is heated to 100～600 DEG C, reacts 2～48h, stop heating and be down to room temperature, it is thus achieved that reaction mixture；
Gained reaction mixture carries out solid-liquid separation, and gained solid is catalyst, is recycled use；Gained filtrate is through subtracting Pressure fractionating obtains unreacted pyridine and target product 2,2 '-bipyridyl.
In above-mentioned synthetic method: M1-M2@Al2O3It is 1:1-10000, preferably 1:4-50 with the mass ratio of pyridine.
Reaction temperature is preferably 400 DEG C, and the response time is preferably 8h.
Described load type double-metal nanocatalyst M1-M2@Al2O3With Al2O3For carrier, with any two kinds of different metal M1 And M2For active component；Wherein M1And M2It is independently selected from precious metals pd, Pt, Ru, Au, Ag, Rh, or non- Noble metal Ni, Cu, Fe, Zn, Co.Noble metal preferred Pd, Pt or Ru；Preferred Cu or Ni of base metal；
The carrier of catalyst can make the Al of various crystal formation2O3, such as α-Al2O3、β-Al2O3、γ-Al2O3With unformed Al2O3, Preferably α-Al2O3、β-Al2O3、γ-Al2O3；
Described active component M1、M2The mol ratio of two kinds of metals is 1:0.01-100；It is total that described active component quality accounts for catalyst The ratio of quality is 5-60%, preferably 30-50%；
Catalyst M in the present invention1-M2@Al2O3The noble metal active component of middle correspondence be the mineral acid by corresponding ion or Acylate or metallo-organic compound etc. convert as precursor and obtain；Such as RuCl3·3H2O、 RuO2、(NH4)2RuCl6、[(C6H5)3P]3RuCl2, acetylacetone,2,4-pentanedione ruthenium, H2PtCl6·6H2O、PtCl4、PtCl3、 PtCl2、[Pt(NH3)4](NO3)2、(NH4)2PtCl6、Pt(NO3)2、(NH4)2PtCl4, acetylacetone,2,4-pentanedione platinum, Pd (NO3)2、Pd(OAc)2、 PdCl2、Pd(OH)2、PdSO4·2H2O、Pd(NH3)2Cl2、Pd(NH3)4Cl2, palladium acetylacetonate, (NH4)2PdCl4、Rh2O3、 RhCl3·3H2O、Rh(OAc)3、Rh(NO3)3Solution, Ru2(SO4)3Solution, (NH4)3RhCl6；Preferably its acetate and chlorine Compound；
M in the present invention1-M2@Al2O3Base metal active component corresponding in catalyst is the mineral acid by corresponding ion Or acylate or metallo-organic compound etc. convert as precursor and obtain；Such as Cu (NO3)2·3H2O、CuCl2·2H2O、 CuO、Cu2O、Cu(OAc)2、Cu2(OH)2CO3, acetylacetone copper, trimethoxy copper, C4H6O4Co、CoCO3、 CoCl2、CoSO4·7H2O、Co(OH)2、Co(NO3)2、CoF2、CoCl2(NH3)4, cobalt naphthenate, acetylacetone cobalt, FeCl3、 FeS、Fe2(C2O4)3·5H2O、Fe(NO3)3、Fe2O3、Fe3O4, ferrocene, trimethoxy ferrum, FeNH4(SO4)2·12H2O、 Ferric acetyl acetonade, NiCl2、C4H6NiO4·4H2O、Ni(OH)2、NiSO4、Ni2O3、NiCO3、Ni(OH)3、Ni(NO3)2、 Nickel acetylacetonate；Preferably its hydrochlorate, nitrate；
The preparation method of load type double-metal nanocatalyst of the present invention, can be nano-particle load method or original position load method.
The step of nano-particle load method is: buy commercially available or self-control alloy nanoparticle M1-M2, according to outside alloy nanoparticle The kind of burden agent and character, select suitable solvent (such as deionized water, alcohol, ether, preferably water and alcohol), preparation uniformly and The alloy nanoparticle dispersion soln of stable dispersion.Take appropriate above-mentioned solution according to required ratio, add certain mass mark Carrier, and after being constantly uniformly mixed, be dried under the conditions of proper temperature and slough solvent, roasting under high temperature after grinding, also Former, annealing, obtains load type double-metal nanometer alloy catalyst.
Load method is prepared the step of catalyst and is in situ: weigh precursor raw material according to the proportioning of active component, with water or the most molten Agent dissolve, stirring, weigh carrier according still further to proportioning and join in above-mentioned solution, stirring a period of time to the most thick, with After under the conditions of proper temperature be dried slough solvent, roasting under high temperature after grinding, reduce, annealing obtains this load type double-metal Nanometer alloy catalyst.
Beneficial effects of the present invention is embodied in:
1, load type double-metal nanocatalyst is applied in the direct coupling production of pyridine 2 by the present invention, in 2 '-bipyridyl, produces effect Rate is high, meets Chemical Manufacture Atom economic principle, does not produce environmentally harmful pollution, is that green chemical industry intermediate produces skill Art.
2, in the synthetic method of the present invention, reclaiming pyridine through vacuum fractionation, the response rate reaches up to 90-98%, pyridine purity 98-99.5%, after distillation, pyridine can utilize with direct circulation；After catalyst reclaims simultaneously, as the case may be, directly repeat to make With or simple dry regeneration and reuse, still keep higher catalysis activity and selectivity of product.
3, in the load type double-metal nanocatalyst of the present invention, double activated component can effectively regulate fracture and the C-C of c h bond The coupling of key, thus improve the activity of catalyst；Use α-Al2O3、β-Al2O3With γ-Al2O3For carrier, specific surface area is big, And the interaction between each active component is strong so that active component is stable on carrier, easily facilitates recovery and reuses.
Four, detailed description of the invention
By following example, the invention will be further described.
Embodiment 1: load method Pd@γ-Al in situ2O3The preparation of metal nano catalyst and catalytic reaction
(1) preparation of catalyst
Weigh 2.00g PdCl2Putting in container, add deionized water 20mL, stirring is to being completely dissolved；Weigh 4g γ-Al2O3 Joining in above-mentioned solution, stirring 4h becomes pasty state, is dried 12h at 75 DEG C, grinds uniformly, will grind after taking out above-mentioned solid Granule after mill is (volume ratio of nitrogen and hydrogen is 1:1) 450 DEG C of activation processing 4h in nitrogen and hydrogen mixture atmosphere, i.e. obtain 5.03g load type metal nanocatalyst Pd@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 4g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 34.8g, and the response rate is 95%, Content detection is 98.5%, obtains 2,2 '-bipyridyl 3.4g, yield 8.5%.
Embodiment 2: load method Cu@γ Al in situ2O3The preparation of metal nano catalyst and catalytic reaction
(1) preparation of catalyst
Weigh 5.34g CuCl2·2H2O puts in container, adds deionized water 20mL, and stirring is to being completely dissolved；Weigh 5g γ-Al2O3Joining in above-mentioned solution, stirring 4h becomes pasty state, is dried 12h at 75 DEG C, grinds uniformly after taking out above-mentioned solid, Granule (volume ratio of nitrogen and hydrogen is 1:1) 450 DEG C of activation processing 5h in nitrogen and hydrogen mixture atmosphere after grinding, to obtain final product To 6.89g load type metal nanocatalyst Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 4g step (1) prepared and 30g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 10h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate contains trace 2,2 '-bipyridyl after testing.Filtrate is through vacuum fractionation Filtrate is reclaimed and is obtained pyridine 28.2g, and the response rate is 94%, and content detection is 97.5%, does not obtain 2,2 '-bipyridyl product.
Embodiment 3: load method Pd-Ni@γ-Al in situ2O3The preparation of (Pd and Ni mol ratio is 2:1) bimetal nano catalyst And catalytic reaction
(1) preparation of catalyst
Weigh 2.34g PdCl2With 1.92g Ni (NO3)2·6H2O puts in container, adds deionized water 30mL, and stirring is to complete CL；Weigh 4g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, in taking-up Grind uniformly after stating solid, granule (volume ratio of nitrogen and hydrogen is 1:1) 500 DEG C in nitrogen and hydrogen mixture atmosphere after grinding Activation processing 5.5h, i.e. obtains 5.59g load type double-metal nanocatalyst Pd-Ni@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 5.0g step (1) prepared and 50g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 22.0g, and the response rate is 92%, Content detection is 95.7%；Obtain 2,2 '-bipyridyl 25.9g, yield 52%.
Embodiment 4: load method Pd-Ni@γ-Al in situ2O3The preparation of (Pd and Ni mol ratio is 1:1) bimetal nano catalyst And catalytic reaction:
(1) preparation of catalyst
Weigh 2.34g PdCl2With 3.84g Ni (NO3)2·6H2O puts in container, adds deionized water 30mL, and stirring is to complete CL；Weigh 4g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, in taking-up Grind uniformly after stating solid, granule (volume ratio of nitrogen and hydrogen is 1:1) 500 DEG C in nitrogen and hydrogen mixture atmosphere after grinding, Activation processing 5.5h, i.e. obtains 5.94g load type double-metal nanocatalyst Pd-Ni@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 5.0g step (1) prepared and 50g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 34.1g, and the response rate is 94%, Content detection is 96.6%；Obtain 2,2 '-bipyridyl 13.5g, yield 27%.
Embodiment 5: load method Pd-Cu@γ-Al in situ2O3The preparation of (Pd and Cu mol ratio is 3:1) bimetal nano catalyst And catalytic reaction:
(1) preparation of catalyst
Weigh 2.50g PdCl2With 0.81g CuCl2·2H2O puts in container, adds deionized water 30mL, and stirring is to the most molten Solve；Weigh 5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, take out above-mentioned solid Grind uniformly after body, granule (volume ratio of nitrogen and hydrogen is 1:1) the 480 DEG C of work in nitrogen and hydrogen mixture atmosphere after grinding Change processes 4.5h, i.e. obtains 6.58g load type double-metal nanocatalyst Pd-Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 5g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 9h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 25.2g, and the response rate is 92%, Content detection is 96.1%；Obtain 2,2 '-bipyridyl 12.1g, yield 30%.
Embodiment 6: load method Pd-Cu@γ-Al in situ2O3The preparation of (Pd and Cu mol ratio is 1:1) bimetal nano catalyst And catalytic reaction:
(1) preparation of catalyst
Weigh 2.50g PdCl2With 2.41g CuCl2·2H2O puts in container, adds deionized water 30mL, and stirring is to the most molten Solve；Weigh 5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, take out above-mentioned solid Grind uniformly after body, granule (volume ratio of nitrogen and hydrogen is 1:1) the 480 DEG C of work in nitrogen and hydrogen mixture atmosphere after grinding Change processes 4.5h, i.e. obtains 7.12g load type double-metal nanocatalyst Pd-Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 5g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 9h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 29.6g, and the response rate is 95%, Content detection is 97.2%；Obtain 2,2 '-bipyridyl 8.4g, yield 21%.
Embodiment 7: load method Ru-Cu@γ-Al in situ2O3The preparation of (Ru and Cu mol ratio is 1:1) bimetal nano catalyst And catalytic reaction:
(1) preparation of catalyst
Weigh 3.69g RuCl2·3H2O and 3.05g CuCl2·2H2O puts in container, adds deionized water 25mL, and stirring is extremely It is completely dissolved；Weigh 4.5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, take Grind uniformly after going out above-mentioned solid, the granule (volume ratio of nitrogen and hydrogen is 1:1) in nitrogen and hydrogen mixture atmosphere after grinding Temperature is 500 DEG C, activation processing 4h, i.e. obtains 7.21g load type double-metal nanocatalyst Ru-Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 5g step (1) prepared and 50g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 10h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 33.38g, and the response rate is 92 %, content detection is 96.7%；Obtain 2,2 '-bipyridyl 13.4g, yield 26.7%.
Embodiment 8: load method Pt-Cu@γ-Al in situ2O3The system of (Pt and Cu mol ratio is 1.5:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst: weigh 2.66g chloroplatinic acid and 0.58g CuCl2·2H2O puts in container, adds deionization Water 20mL, stirring is to being completely dissolved；Weigh 4g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C Under be dried 12h, take out and grind after above-mentioned solid uniformly, the granule after grinding in nitrogen and hydrogen mixture atmosphere (nitrogen and hydrogen Volume ratio is 1:1) 450 DEG C of activation processing 5h, i.e. obtain 5.08g load type double-metal nanocatalyst Pt-Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized:
Catalyst 4.5g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 31.2g, and the response rate is 90%, Content detection is 95.9%；Obtain 2,2 '-bipyridyl 4.68g, yield 11.7%.
Embodiment 9: load method Ru-Ni@γ-Al in situ2O3The system of (mol ratio of Ru and Ni is 2:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst
Weigh 3.07g RuCl2·3H2O and 2.16g Ni (NO3)2·6H2O puts in container, adds deionized water 25mL, stirs Mix to being completely dissolved；Weigh 5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, Grind uniformly after taking out above-mentioned solid, the granule (volume ratio of nitrogen and hydrogen is 1:1) in nitrogen and hydrogen mixture atmosphere after grinding 550 DEG C of activation processing 5h, i.e. obtain 5.77g load type double-metal nanocatalyst Ru-Ni@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 6g step (1) prepared and 35g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 26.2g, and the response rate is 91%, Content detection is 97.4%；Obtain 2,2 '-bipyridyl 5.34g, yield 15.3%.
Embodiment 10: nano-particle load method Pd-Ni@γ-Al2O3(3:1) preparation of bimetal nano catalyst and catalytic reaction:
(1) preparation of catalyst
According to list of references [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.] prepare particle diameter about at the Pd-Ni alloy nanoparticle of 10nm (Pd and Ni mol ratio is 3:1) 5g, add Enter water is made into the dispersion soln 20mL (Pd content 30%) of Pd-Ni.4g γ-Al is added in dispersion soln2O3Stirring 3h Mix homogeneously.Mixed solution is put into vacuum drying oven is sloughed under room temperature solvent, roasting at 550 DEG C after grinding, reduction 4h, Annealing obtains support type double nano alloy catalyst Pd-Ni@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 3g step (1) prepared and 30g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 15.7g, and the response rate is 93%, Content detection is 96.3%；Obtain 2,2 '-bipyridyl 12.9g, yield 43.1%.
Embodiment 11: nano-particle load method Pt-Cu@γ-Al2O3(2:1) preparation of bimetal nano catalyst and catalytic reaction:
(1) preparation of catalyst
According to list of references [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 fuelcells.Journalof Power Sources (2016) Pt-Cu alloy nanoparticle (Pd and Cu mol ratio the is 3:1) 5g of particle diameter about 6nm, 316,124-131.] is prepared, It is added to the water the dispersion soln 20mL (Pt content 35%) being made into Pt-Cu.4g γ-Al is added in dispersion soln2O3Stirring 3h Mix homogeneously.Mixed solution is put into vacuum drying oven is sloughed under room temperature solvent, roasting at 400 DEG C after grinding, reduction 5h, Annealing obtains support type double nano alloy catalyst Pt-Cu@γ-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 3g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 10h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 30.2g, and the response rate is 94%, Content detection is 95.9%.Obtain 2,2 '-bipyridyl 7.24g, yield 18.1%.
Embodiment 12: load method Pt-Pd@γ-Al in situ2O3The preparation of (Pt and Pd mol ratio is 1:1) bimetal nano catalyst And catalytic reaction:
(1) preparation of catalyst
Weigh 2.66g chloroplatinic acid and 0.91g PdCl2Putting in container, add deionized water 20mL, stirring is to being completely dissolved； Weigh 5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, after taking out above-mentioned solid Grinding uniformly, the granule after grinding is in nitrogen and hydrogen mixture atmosphere at (volume ratio of nitrogen and hydrogen is 1:1) 380 DEG C of activation Reason 3.5h, i.e. obtains 6.41g load type double-metal nanocatalyst Pt-Pd@γ-Al2O3。
(2) catalytic pyridine direct coupling synthesis 2,2 '-bipyridyl
Catalyst 5g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate and return Receiving catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 30.1g, and the response rate is 94%, Content detection is 93.7%；Obtain 2,2 '-bipyridyl 7.32g, yield 18.3%.
Embodiment 13: load method Pt-Pd@γ-Al in situ2O3The system of (mol ratio of Pt and Pd is 2:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst
Weigh 5.32g chloroplatinic acid and 0.91g PdCl2Putting in container, add deionized water 25mL, stirring is to being completely dissolved； Weigh 5g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, after taking out above-mentioned solid Grinding uniformly, granule (volume ratio of nitrogen and hydrogen the is 1:1) temperature in nitrogen and hydrogen mixture atmosphere after grinding is 380 DEG C, Activation processing 3.5h, i.e. obtains 7.31g load type double-metal nanocatalyst Pt-Pd@γ-Al2O3。
(2) 2 are catalyzed and synthesized, 2 '-bipyridyl
Catalyst 5g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 28.3g, and the response rate is 93%, Content detection is 95.9%；Obtain 2,2 '-bipyridyl 9.04g, yield 22.6%.
Embodiment 14: load method Cu-Ni@γ-Al in situ2O3The system of (mol ratio of Cu and Ni is 1:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst
Weigh 3.21g CuCl2·3H2O and 5.45g Ni (NO3)2·6H2O puts in container, adds deionized water 25mL, stirs Mix to being completely dissolved；Weigh 4g γ-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, Grind uniformly after taking out above-mentioned solid, the granule (volume ratio of nitrogen and hydrogen is 1:1) in nitrogen and hydrogen mixture atmosphere after grinding 600 DEG C of activation processing 7h, i.e. obtain 6.18g support type Cu-Ni@γ-Al2O3Metal nano catalyst.
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 3g step (1) prepared and 60g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and separate And reclaiming catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 52.7g, and the response rate is 93%, Content detection is 95.0%；Obtain 2,2 '-bipyridyl 3.48g, yield 5.8%.
Embodiment 15: load method Pd-Ni@α-Al in situ2O3The system of (mol ratio of Pd and Ni is 2:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst
Weigh 2.34g PdCl2With 1.92g Ni (NO3)2·6H2O puts in container, adds deionized water 30mL, and stirring is to complete CL；Weigh 4g α-Al2O3, join and above-mentioned solution stir 4h one-tenth pasty state, at 75 DEG C, be dried 12h, in taking-up Grind uniformly after stating solid, granule (volume ratio of nitrogen and hydrogen is 1:1) 500 DEG C in nitrogen and hydrogen mixture atmosphere after grinding Activation processing 5.5h, i.e. obtains 6.59g load type double-metal nanocatalyst Pd-Ni@α-Al2O3。
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 4g step (1) prepared and 40g pyridine add in autoclave, use N2Replace O therein2After, Sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped after reaction 8h, to still temperature drop to room temperature, Open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and be separated and recovered from urging Agent, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 24.3g, and the response rate is 90%, content It is detected as 94.8%；Obtain 2,2 '-bipyridyl 12.4g, yield 31.0%.
Embodiment 16: load method Pd-Ni@γ-Al in situ2O3The system of (mol ratio of Pd and Ni is 2:1) bimetal nano catalyst Standby and catalytic reaction:
(1) preparation of catalyst is with embodiment 3
(2) catalysis 4-picoline synthesis 4,4 '-dimethyl-2,2 '-bipyridyl
Catalyst 5.0g step (1) prepared and 4-picoline 50g adds in autoclave, uses N2Displacement is wherein O2After, sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Heating is stopped, to still after reaction 11h Temperature drop, to room temperature, opens autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter Being separated and recovered from catalyst, catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained 4-picoline 31.1g, The response rate is 90%, and content detection is 96.1%.4,4 '-dimethyl-2,2 '-bipyridyl 14.8g, yield 29.6%.
Embodiment 17, pyridine the synthesis 2,2 '-bipyridyl reclaimed
(1) preparation of catalyst is with embodiment 3；
(2) 2,2 '-bipyridyl is catalyzed and synthesized
Catalyst 2.5g step (1) prepared and the pyridine 20g (content >=98.0%) of recovery adds in autoclave, Use N2Replace O therein2After, sealed reactor；Unlatching autoclave stirs, and is heated to still temperature 400 DEG C；Stop after reaction 8h Only heating, to still temperature drop to room temperature, opens autoclave valve, the H that safety dumping reaction generates2.Reaction is taken out from autoclave Mixed liquor, filters and is separated and recovered from catalyst, and catalyst can utilize by direct circulation.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 9.05 G, the response rate is 91%, and content detection is 94.6%；Obtain 2,2 '-bipyridyl 10.02g, yield 50.1%.
Embodiment 18, recovery catalyst performance research
(1) catalyst is the catalyst that embodiment 3 reclaims
(2) 2,2 '-bipyridyl is catalyzed and synthesized
The catalyst 3g that will reclaim in pyridine 30g and embodiment 3, adds in autoclave, uses N2Replace O therein2 After, sealed reactor；Unlatching autoclave stirs, and is heated to still temperature to 400 DEG C；Heating is stopped, to still temperature drop after reaction 8h Low to room temperature, open autoclave valve, the H that safety dumping reaction generates2.From autoclave, take out reaction mixture, filter and divide From and reclaim catalyst, catalyst can direct circulation utilize.Filtrate is reclaimed through vacuum fractionation and is obtained pyridine 13.9g, and the response rate is 92%, content detection is 95.8%；Obtain 2,2 '-bipyridyl 14.55g, yield 48.2%.

Claims (5)

1. use the 2 of load type double-metal nanocatalyst, the synthetic method of 2 '-bipyridyl, it is characterised in that: double with support type Metal nano catalyst M1-M2@Al2O3For catalyst, catalytic pyridine direct coupling reaction synthesis 2,2 '-bipyridyl, reaction side Shown in formula such as formula (1):
R in formula1、R2、R3、R4It is independently selected from H, methyl, ethyl, propyl group, butyl, amyl group or hexyl；
Described load type double-metal nanocatalyst M1-M2@Al2O3It is with Al2O3For carrier, with any two kinds of different metals M1And M2Catalyst for active component；Wherein M1And M2Be independently selected from precious metals pd, Pt, Ru, Au, Ag, Rh, or non-noble metal Ni, Cu, Fe, Zn, Co.
Synthetic method the most according to claim 1, it is characterised in that be to carry out as follows:
By M1-M2@Al2O3Join in autoclave, and add pyridine, use N2O in displacement autoclave2After, Sealed reactor；It is heated to 100～600 DEG C, reacts 2～48h, stop heating and be down to room temperature, it is thus achieved that reaction mixture；
Carrying out gained reaction mixture filtering and separate, gained solid is catalyst, is recycled use；Gained filtrate is through subtracting Pressure fractionating obtains unreacted pyridine and target product 2,2 '-bipyridyl.
Synthetic method the most according to claim 2, it is characterised in that: M1-M2@Al2O3It is 1 with the mass ratio of pyridine: 1-10000。
Synthetic method the most according to claim 3, it is characterised in that: M1-M2@Al2O3It is 1:4 with the mass ratio of pyridine -50。
Synthetic method the most according to claim 2, it is characterised in that: reaction temperature is 400 DEG C, and the response time is 8h.
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