CN110801841A - Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof - Google Patents

Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof Download PDF

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CN110801841A
CN110801841A CN201911177344.9A CN201911177344A CN110801841A CN 110801841 A CN110801841 A CN 110801841A CN 201911177344 A CN201911177344 A CN 201911177344A CN 110801841 A CN110801841 A CN 110801841A
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catalyst
pyridine
preparing
bipyridine
nickel
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王玉忠
刘盛林
徐龙伢
朱向学
李秀杰
谢素娟
陈福存
张爽
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention provides a catalyst for preparing 2, 2' -bipyridyl by coupling synthesis of pyridine, a preparation method and application thereof. During the impregnation process, L-arginine, Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and the like are added to promote the dispersion of the metal. The catalyst can realize the continuous reaction of preparing 2, 2' -bipyridyl by pyridine coupling in a fixed bed reactor.

Description

Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalyst for preparing 2, 2' -bipyridine by pyridine coupling, a preparation method and application thereof.
Background
2, 2' -dipyridyl is an important intermediate for fine chemical engineering and drug synthesis, and is a unique chelating agent for detecting indicators of metal ions, photosensitizers, ligands of metal organic catalysts and the like. Especially in recent years, with the banning of the highly toxic herbicide paraquat, the synthesis and production of diquat, a herbicide containing lower toxicity, will be on the rise of an important schedule. The synthetic raw material of the diquat is mainly 2, 2' -bipyridine, so the product has important social significance and industrial application prospect for the development of pyridine downstream products, especially the development and production of low-toxicity pesticides.
At present, the production process for producing 2, 2' -bipyridine in China mainly takes pyridine as a raw material, and comprises chlorination and coupling. Chinese patent CN103172559A reports that 2, 2' -bipyridine is synthesized by taking 2-chloropyridine as a raw material and taking triphenylphosphine, zinc powder and nickel chloride as three-component catalysts. Although the process can obtain higher product yield, the catalyst is difficult to separate from the product, the catalyst is inconvenient to recycle, the steps are complicated, the production period is long, and the most main problems are that virulent chlorine is involved in the production process, so that great potential safety hazards exist, equipment is greatly corroded, and the environment is seriously polluted.
Chinese patent CN105461620A discloses a Raney nickel catalytic preparation method of 2,2 '-bipyridine, which directly takes pyridine as a raw material and Raney nickel as a catalyst to carry out pyridine coupling to prepare the 2, 2' -bipyridine. The method is clean and environment-friendly, and pyridine which does not participate in the reaction can be recycled. However, the preparation and the use of the Raney nickel catalyst have great safety problems, and meanwhile, the process adopts a kettle type reactor, so that continuous reaction and production cannot be realized like a fixed bed reactor.
Due to the development of reaction conditions and equipment, a device similar to a Soxhlet extractor is produced, and the method is improved in that 2,2 ' -bipyridine is separated from a catalyst immediately after being produced, so that the service life of the catalyst is prolonged, and the yield of the product 2,2 ' -bipyridine is improved to a certain extent, namely 0.0231g of 2,2 ' -bipyridine/g of Raney nickel/hour (hereinafter, the yield is simplified to be g/g/h), while the yield is only 0.007g/g/h by using the original method.
Gore in the last 90 th century proposed a process for the production of 2, 2' -bipyridine. The method also uses pyridine and Raney nickel catalyst, and controls the reaction temperature between 200 ℃ and 240 ℃ (preferably at 220 ℃ in the experiment), because the reaction temperature is too high to cause the catalyst to lose efficacy quickly, and the reaction yield is reduced because the temperature is too low. The pressure of the system may be controlled so that a part of pyridine is kept in a liquid state.
Disclosure of Invention
The invention aims to provide a novel catalyst for preparing 2, 2' -bipyridyl through coupling synthesis of pyridine, a preparation method and application thereof.
The invention provides a catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine, which is a nickel/alumina catalyst prepared by an impregnation method by taking nickel as a main active component and macroporous alumina as a carrier, wherein the nickel content is 10-30% by weight of the catalyst, and the preferred nickel content is 15-25%. Wherein, the alumina carrier is obtained by modifying silicon oxide and one or more of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid.
The impregnation method is to add a surfactant in the process of impregnating the nickel nitrate. The surfactant is one or more of L-arginine, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone.
The invention provides a preparation method of the catalyst, which comprises the following specific steps:
(1) pretreating the formed alumina carrier containing 0.1-5.0 wt% of silicon oxide, treating the alumina carrier by using 1-5 wt% of acid solution at 80 ℃, washing the alumina carrier by water for 1-2 times, drying the alumina carrier at 120 ℃, and roasting the alumina carrier for 3-5 hours at 400-800 ℃ to obtain a modified alumina carrier; the acid solution is one or a mixture of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid.
(2) Vacuumizing the modified alumina carrier in the step (1) for 1 hour;
(3) preparing a nickel nitrate solution, and adding a surfactant into the solution, wherein the nickel content is 15-30% and the surfactant content is 1% -5% in percentage by weight of the catalyst, so as to obtain an impregnation solution; the surfactant is one or more of L-arginine, Cetyl Trimethyl Ammonium Bromide (CTAB) and polyvinylpyrrolidone (PVP).
(4) Absorbing the prepared impregnation liquid into the modified alumina carrier subjected to vacuum treatment, aging for 1 hour at 80 ℃, drying for 4-8 hours at 80 ℃, drying for 6-12 hours at 120 ℃, and roasting for 3 hours at 600 ℃ at 300-;
(5) and (3) introducing hydrogen into the product obtained in the step (4) to reduce the product at the temperature of 200-550 ℃ for 2-10 hours to obtain the nickel/alumina catalyst.
The catalyst provided by the invention can be used in a continuous fixed bed reactor to realize direct coupling of pyridine to prepare 2, 2' -bipyridine, and has high activity and stability. Without the need for a first chlorination and then dechlorination coupling operation of the pyridine.
The invention has the advantages that: the alumina carrier after acid treatment and the addition of the activator in the preparation process can highly disperse the active component nickel of the catalyst, and has the characteristics of high activity, good stability and the like in the reaction process of preparing 2, 2' -bipyridine by pyridine coupling. Under the action of the catalyst, the pyridine can be directly coupled to prepare the 2, 2' -bipyridine by adopting a continuous fixed bed process, the pyridine is not required to be firstly chlorinated and then dechlorinated and coupled, and the catalyst is green and environment-friendly and does not need corrosion-resistant equipment.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
Treating a spherical alumina carrier containing 3.0% of silicon oxide by one or more of 3% of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid at 80 ℃, washing the alumina carrier with water for 1 to 2 times, drying the alumina carrier at 120 ℃, and roasting the alumina carrier at 650 ℃ for 3 hours to obtain a catalyst carrier;
weighing nickel nitrate and polyvinylpyrrolidone according to the content of an active component nickel, dissolving the nickel nitrate and the polyvinylpyrrolidone in water to prepare a solution, vacuumizing the modified alumina carrier, absorbing impregnation liquid into the carrier by adopting a conventional impregnation method, aging at 80 ℃ for 2 hours, drying at 80 ℃ for 6 hours, drying at 120 ℃ for 12 hours, and roasting at 450 ℃ for 3 hours; introducing hydrogen into the calcined catalyst to reduce the catalyst for 5 hours at 550 ℃.
Catalyst a prepared in this example contains 21% nickel, and 5% polyvinylpyrrolidone is added to the impregnation solution.
Example 2
Catalyst B was prepared in the same manner as in example 1, except that the nickel content of the catalyst was 25%, and 2% cetyltrimethylammonium bromide (CTAB) and 3% polyvinylpyrrolidone (PVP) were added to the impregnation solution.
Example 3
Catalyst C was prepared in the same manner as in example 1, except that the nickel content of the catalyst was 30% and 5% polyvinylpyrrolidone (PVP) was added to the impregnation solution.
Example 4
Catalyst D was prepared in the same manner as in example 1, except that the nickel content of the catalyst was 15% and 3% L-arginine was added to the impregnation solution.
Comparative example 1
Catalyst E was prepared in the same manner as in example 1, except that the alumina support was not treated with one or more of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid, the nickel content of the catalyst was 21%, and no surfactant was added to the impregnation solution.
Example 5
The catalyst performance test is carried out in a self-made small-scale reaction device. The diameter of the reactor is 14mm, the catalyst loading is 2.5g, the reaction pressure is 1.0MPa, the reaction temperature is 200 ℃, and the pyridine mass space velocity is 8h-1。
The product was analyzed by Walian 3800 chromatography, FID detector, HP-5 capillary column. The specific evaluation results are shown in Table 1.
TABLE 1 evaluation results of catalysts
Catalyst and process for preparing same Nickel content Catalyst efficiency
A 21％ 0.378g 2, 2' -bipyridine/g catalyst/h
B 25％ 0.362g 2, 2' -bipyridine/g catalyst/h
C 30％ 0.258g of 2, 2' -bipyridine/g of catalyst/h
D 15％ 0.357g 2, 2' -bipyridine/g catalyst/h
E 21％ 0.078g 2, 2' -bipyridine/g catalyst/h
Example 6
Under typical reaction conditions, the catalyst A of the present invention was subjected to a pilot test evaluation of 334Kg under a continuous fixed bed reactor, and the results are shown in Table 2. According to the evaluation results, 40 tons of 2, 2' -bipyridine per ton of the catalyst was produced by calculation.
TABLE 2 Pilot experimental results for catalyst A of the invention
Figure BDA0002290316180000051

Claims (10)

1. A catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine is characterized in that the catalyst is a nickel/alumina catalyst prepared by taking nickel as a main active component and modified macroporous alumina as a carrier and adopting an impregnation method, wherein the nickel content is 10-30% by weight of the catalyst.
2. The catalyst of claim 1, wherein the catalyst is used for preparing 2, 2' -bipyridine by pyridine coupling, and the catalyst comprises: the nickel content is 15-25% by weight of the catalyst.
3. The catalyst of claim 1, wherein the modified alumina support is obtained by modifying silica and one or more of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid.
4. The catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine according to claim 1, wherein: the impregnation method is to add a surfactant in the process of impregnating the nickel nitrate.
5. The catalyst for the coupling preparation of 2, 2' -bipyridine by synthesis of pyridine according to claim 4, characterized in that: the surfactant is one or more of L-arginine, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone.
6. A method for preparing the catalyst according to any one of claims 1 to 5, comprising the following steps:
(1) pretreating the formed alumina carrier containing 0.1-5.0 wt% of silicon oxide, treating the alumina carrier by using 1-5 wt% of acid solution at 80 ℃, washing the alumina carrier by water for 1-2 times, drying the alumina carrier at 120 ℃, and roasting the alumina carrier for 3-5 hours at 400-800 ℃ to obtain a modified alumina carrier;
(2) vacuumizing the modified alumina carrier in the step (1) for 1 hour;
(3) preparing a nickel nitrate solution, and adding a surfactant into the solution, wherein the nickel content is 15-30% and the surfactant content is 1% -5% in percentage by weight of the catalyst, so as to obtain an impregnation solution;
(4) absorbing the prepared impregnation liquid into the modified alumina carrier subjected to vacuum treatment, aging for 1 hour at 80 ℃, drying for 4-8 hours at 80 ℃, drying for 6-12 hours at 120 ℃, and roasting for 3 hours at 600 ℃ at 300-;
(5) and (3) introducing hydrogen into the product obtained in the step (4) to reduce the product at the temperature of 200-550 ℃ for 2-10 hours to obtain the nickel/alumina catalyst.
7. The method for preparing a catalyst according to claim 6, characterized in that: the acid solution is one or a mixture of oxalic acid, nitric acid, sulfuric acid and hydrochloric acid.
8. The method for preparing a catalyst according to claim 6, characterized in that: the surfactant is one or more of L-arginine, Cetyl Trimethyl Ammonium Bromide (CTAB) and polyvinylpyrrolidone (PVP).
9. Use of a catalyst according to any one of claims 1 to 5, wherein the catalyst is used in a continuous fixed bed reactor for the direct coupling of pyridine to 2, 2' -bipyridine, and the catalyst exhibits high activity and stability.
10. Use of the catalyst according to claim 9, characterized in that the pyridine is not required to be chlorinated and then dechlorinated for coupling.
CN201911177344.9A 2019-11-27 2019-11-27 Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof Pending CN110801841A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN111992221A (en) * 2020-08-14 2020-11-27 东南大学 Three-dimensional hollow high-dispersion metal catalyst and preparation method thereof
CN115279491A (en) * 2020-05-14 2022-11-01 庄信万丰股份有限公司 Catalyst for biaryl production
CN115417809A (en) * 2022-09-05 2022-12-02 天津药明康德新药开发有限公司 Preparation method of 4, 4-dipyrrole-2, 2-bipyridine
CN115779912A (en) * 2022-12-20 2023-03-14 西安凯立新材料股份有限公司 Catalyst for synthesizing 2, 2-bipyridine by one-step method and preparation method and application thereof

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN115279491A (en) * 2020-05-14 2022-11-01 庄信万丰股份有限公司 Catalyst for biaryl production
CN115279491B (en) * 2020-05-14 2023-12-12 庄信万丰股份有限公司 Catalyst for biaryl production
CN111992221A (en) * 2020-08-14 2020-11-27 东南大学 Three-dimensional hollow high-dispersion metal catalyst and preparation method thereof
CN111992221B (en) * 2020-08-14 2022-04-26 东南大学 Three-dimensional hollow high-dispersion metal catalyst and preparation method thereof
CN115417809A (en) * 2022-09-05 2022-12-02 天津药明康德新药开发有限公司 Preparation method of 4, 4-dipyrrole-2, 2-bipyridine
CN115779912A (en) * 2022-12-20 2023-03-14 西安凯立新材料股份有限公司 Catalyst for synthesizing 2, 2-bipyridine by one-step method and preparation method and application thereof

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