CN112604706B - Preparation method and application of Co@CN catalyst derived from nitrogen-containing super-crosslinked polymer - Google Patents

Preparation method and application of Co@CN catalyst derived from nitrogen-containing super-crosslinked polymer Download PDF

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CN112604706B
CN112604706B CN202110051682.9A CN202110051682A CN112604706B CN 112604706 B CN112604706 B CN 112604706B CN 202110051682 A CN202110051682 A CN 202110051682A CN 112604706 B CN112604706 B CN 112604706B
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nitrogen
crosslinked polymer
catalyst
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CN112604706A (en
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张华新
张丽丽
王洪林
杨红梅
李立威
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Jingchu University of Technology
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method and application of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer. The preparation method comprises the following steps: and (3) dissolving the benzo nitrogen-containing heterocyclic compound, benzene, dimethoxymethane and anhydrous ferric trichloride in an organic solvent, heating to fully react, purifying and drying the resultant to obtain the nitrogen-containing super-crosslinked polymer. Then dispersing the polymer and cobalt salt into deionized water, adding urea, transferring to a reaction kettle, performing heat treatment under a turnover condition, cooling, separating, washing, drying and purifying to obtain a precursor. And finally, pyrolyzing the precursor in a nitrogen atmosphere to prepare a high-catalytic-activity nitrogen-containing super-crosslinked polymer-derived Co@CN catalyst, and using the catalyst in a reaction for preparing tetrahydroquinoline compounds by catalyzing selective hydrogenation of quinoline compounds. The invention improves the yield of the quinoline compound for preparing the tetrahydroquinoline compound and reduces the reaction temperature.

Description

Preparation method and application of Co@CN catalyst derived from nitrogen-containing super-crosslinked polymer
Technical Field
The invention belongs to the technical field of quinoline selective hydrogenation catalyst synthesis, and relates to a preparation method and application of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer.
Background
The 1,2, 3, 4-tetrahydroquinoline compound is an active component of a plurality of natural substances, is an important nitrogenous heterocyclic compound, has various important biological activities such as antioxidation, antibiosis, anti-tumor and the like, and can be used for inhibiting glutamate toxicity and lipid peroxidation, and preventing and treating diseases such as tumor, thrombus, arrhythmia and the like; the method can be used as a raw material for synthesizing chiral drugs such as natural alkaloids, and the research on the synthesis method thereof has been attracting attention. The synthesis methods of tetrahydroquinoline are many, such as aza Michael addition reaction, amino halogenation reaction, allylamine reaction, hydrolysis reaction, nucleophilic substitution reaction, amidation reaction, hydrogenation reduction reaction, oxidative cyclization/lactic acid reaction, cross coupling reaction, etc., but because quinoline is easy to obtain, quinoline can be industrially used to prepare 1,2, 3, 4-tetrahydroquinoline by catalytic hydrogenation, so the development of hydrogenation catalyst is very critical.
At present, the catalysts for preparing the 1,2, 3, 4-tetrahydroquinoline compounds by selective hydrogenation of quinoline compounds, which have been developed and reported, mainly adopt noble metals such as Au, ru, pd and the like (Adv Synth catalyst, 2015, 357,753; nano Research 2016, 9, 2632; CN 107824209A), and have high preparation and use costs, and are not beneficial to industrial application. The Chinese patent publication No. CN109759134A discloses a Cu@C catalyst derived from MOFs, and the noble metal is avoided, but a simple carbon material matrix has a weak effect of promoting electron transfer in a catalytic process, so that a catalytic reaction requires a higher temperature to obtain a better conversion rate.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing the high-activity reusable Co@CN catalyst by assembling non-noble metal cobalt by using a nitrogen-containing super-crosslinked polymer and preparing the 1,2, 3, 4-tetrahydroquinoline compound by catalyzing the selective hydrogenation reaction of the quinoline compound by pyrolysis, so that the activity of the catalyst is effectively improved, and the preparation and use cost of the catalyst are reduced.
The technical problems to be solved by the invention are realized by the following technical proposal.
The preparation method of the Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer comprises the following steps:
s1, dissolving a benzazepine heterocyclic compound, benzene, dimethoxymethane and anhydrous ferric trichloride in an organic solvent, heating to fully react, purifying and drying a resultant to obtain a nitrogen-containing super-crosslinked polymer;
s2, dispersing the polymer and cobalt salt into deionized water, adding urea, transferring to a reaction kettle, performing heat treatment under a turnover condition, cooling, separating, washing and drying to obtain a precursor;
s3, pyrolyzing the precursor in a nitrogen atmosphere to prepare the Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer with high catalytic activity.
The benzoazepine compound in S1 is selected from one or more of benzimidazole and benzotriazole; the adding molar ratio of the benzonitrogen heterocyclic compound to benzene is 1 (0.1-10); the molar ratio of the total amount of the benzazepine heterocyclic compound and benzene to the dimethoxymethane is 1 (1-4).
The organic solvent in S1 is selected from one or more of 1, 2-dichloroethane, dichloromethane, chloroform, carbon tetrachloride and cyclohexane.
The specific steps of purifying the product in S1 are as follows: and carrying out Soxhlet extraction on the product for 10-24 hours by using methanol or ethanol.
And S2, the cobalt salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate.
The heat treatment under the overturning condition in S2 is specifically as follows: and fixing the sealed high-pressure reaction kettle on a rotating shaft of the homogeneous phase reactor for overturning, wherein the rotating speed is 40-100 rpm, the temperature is 110-180 ℃, and the treatment time is 4-10 hours.
The pyrolysis under the nitrogen atmosphere in S3 is specifically as follows: placing the precursor in a vacuum tube furnace, and adding the precursor into N 2 Under the protection, pyrolyzing 1-4 h in the temperature environment of 400-800 ℃.
An application of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer in the reaction of preparing tetrahydroquinoline compounds by selectively hydrogenating quinoline compounds.
Compared with the prior art, the invention has the beneficial effects that:
1. the Co@CN catalyst prepared by the method avoids using noble metal, effectively reduces the preparation and use costs of the catalyst, and is convenient for large-scale production and application.
2. The Co@CN catalyst prepared by the method is a typical porous material, has a surface area far larger than that of carbon materials derived from MOFs and the like, has a hierarchical pore structure, is beneficial to the diffusion and mass transfer of a reaction system, and is convenient for the active site to fully contact with a substrate.
3. The Co@CN catalyst matrix prepared by the method is an aza-carbon material generated by polymer pyrolysis, and the nitrogen doping can not only enhance the interaction between the matrix and metal and improve the stability of the catalyst, but also effectively improve the electron transfer performance of the catalyst and improve the catalytic reaction activity.
Drawings
FIG. 1 is a powder XRD pattern of a nitrogen-containing super cross-linked polymer derived Co@CN catalyst prepared in example 1.
FIG. 2 is an SEM image of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer prepared in example 1.
FIG. 3 is N of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer prepared in example 1 2 Adsorption-desorption isotherms and DFT pore size distribution plots.
Description of the embodiments
The present invention will be described in detail with reference to the following examples, which are only preferred embodiments of the present invention and are not limiting thereof.
Example 1 ]
A preparation method of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer comprises the following steps:
s1, 10 mmol of benzotriazole, 30 mmol of benzene, 6.5. 6.5 g dimethoxy methane and 9.5 anhydrous ferric trichloride are dissolved in 100 mL of 1, 2-dichloroethane, and the mixture is heated to 80 ℃ to fully react with the mixture for 24 h. The product is subjected to Soxhlet extraction of 24 and h by methanol, impurities are removed, and then the product is dried by spin drying by a rotary evaporator, so that the nitrogen-containing super-crosslinked polymer is obtained.
S2, dispersing the polymer 1 g and 1.48 g cobalt nitrate hexahydrate into 50 mL deionized water, adding 0.5 g urea, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, fixing the sealed high-pressure reaction kettle on a rotating shaft of a homogeneous reactor, overturning at a speed of 60 rpm, setting the temperature to 170 ℃, and treating the treatment time to 9 h. Cooling, filtering, collecting solid, washing with deionized water to neutrality, drying at 80deg.C overnight, and purifying to obtain precursor.
S3, spreading the 500 mg precursor at the bottom of the porcelain boat, placing the porcelain boat in a vacuum tube furnace, and placing the porcelain boat in N 2 Under the protection, the temperature is raised to 600 ℃ at the heating rate of 10 ℃/min, and the pyrolysis is carried out at constant temperature of 2 h. After cooling 290 mg Co@CN catalyst was obtained.
As can be seen from fig. 1, the broad peaks of the polymer in the powder XRD pattern of the co@cn catalyst derived from the nitrogen-containing super-crosslinked polymer prepared in this example disappear, and at the same time, characteristic diffraction peaks of the crystal planes 111, 200 and 220 of the cobalt simple substance appear at the positions of 2θ=44.2 °, 51.5 ° and 44.2 °, which indicates that the decomposition has occurred in the precursor to generate the azacarbon material, and at the same time, the metallic cobalt species is reduced to zero-valent simple substance cobalt.
FIG. 2 shows that the Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer prepared in the embodiment partially retains the structure of the nitrogen-containing super-crosslinked polymer and has a relatively dispersed hollow leaf-shaped morphology.
FIG. 3 shows that the nitrogen-containing super-crosslinked polymer-derived Co@CN catalyst prepared in this example has a BET surface area of 410.6 m 2 And/g, which is far greater than the carbon materials derived from pyrolysis of common MOFs and other materials. At the same time its N 2 The adsorption-desorption isotherm has obvious hysteresis, and the combination of the DFT aperture distribution diagram shows that a large number of mesopores exist in the Co@CN catalyst structure derived from the nitrogen-containing super-crosslinked polymer prepared by the embodiment, which belongs to typical micro-mesopore coexisting hierarchical pore materials and is beneficial to the dispersion of metal sites and the mass transfer diffusion of a reaction system.
The Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer prepared in the embodiment is used for catalyzing the reaction of preparing tetrahydroquinoline by selective hydrogenation of quinoline. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 1 mmol quinoline, 50 mg Co@CN catalyst, 5 mL H 2 O, 3 MPa H 2 100 ℃, 6 h. The conversion rate of quinoline is 100%, the selectivity of 1,2, 3, 4-tetrahydroquinoline is 100% and the conversion rate and the selectivity of quinoline are more than 95% after the catalyst is circulated for 12 times by using an internal standard method.
Example 2 ]
S1, 10 mmol of benzotriazole, 30 mmol of benzene, 6.5. 6.5 g dimethoxy methane and 9.5 anhydrous ferric trichloride are dissolved in 100 mL of 1, 2-dichloroethane, and the mixture is heated to 80 ℃ to fully react with the mixture for 24 h. The product is subjected to Soxhlet extraction of 24 and h by methanol, impurities are removed, and then the product is dried by spin drying by a rotary evaporator, so that the nitrogen-containing super-crosslinked polymer is obtained.
S2, dispersing the polymer 1 g and 0.80 g cobalt acetate into 50 mL deionized water, adding 0.5 g urea, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, fixing the sealed high-pressure reaction kettle on a rotating shaft of a homogeneous reactor, overturning at a speed of 60 rpm, setting the temperature to 170 ℃, and treating the treatment time to 9 h. Cooling, filtering, collecting solid, washing with deionized water to neutrality, drying at 80deg.C overnight, and purifying to obtain precursor.
S3, spreading the 500 mg precursor at the bottom of the porcelain boat, placing the porcelain boat in a vacuum tube furnace, and placing the porcelain boat in N 2 Under the protection, the temperature is raised to 600 ℃ at the heating rate of 10 ℃/min, and the pyrolysis is carried out at constant temperature of 2 h. After cooling 301 mg Co@CN catalyst was obtained.
The Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer prepared in the embodiment is used for catalyzing the reaction of preparing 3-hydroxytetrahydroquinoline by selectively hydrogenating 3-hydroxyquinoline. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 1 mmol 3-hydroxyquinoline, 50 mg Co@CN catalyst, 5 mL H 2 O, 3 MPa H 2 100 ℃, 6 h. The reactants and the products are determined by gas chromatography by an internal standard method, the conversion rate of 3-hydroxyquinoline is 90.1 percent, the selectivity of 3-hydroxytetrahydroquinoline is 100 percent, and the conversion rate of more than 80 percent and the selectivity of 100 percent can be still maintained after the catalyst is circulated for 8 times.
Example 3 ]
A preparation method of a Co@CN catalyst derived from a nitrogen-containing super-crosslinked polymer comprises the following steps:
s1, 10 mmol of benzimidazole, 30 mmol of benzene, 6.5 g dimethoxy methane and 9.5 anhydrous ferric trichloride are dissolved in 100 mL of 1, 2-dichloroethane, and the mixture is heated to 80 ℃ to fully react for 24 h. The product is subjected to Soxhlet extraction of 24 and h by methanol, impurities are removed, and then the product is dried by spin drying by a rotary evaporator, so that the nitrogen-containing super-crosslinked polymer is obtained.
S2, dispersing the polymer 1 g and 1.35 g cobalt nitrate hexahydrate into 50 mL deionized water, adding 0.5 g urea, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, fixing the sealed high-pressure reaction kettle on a rotating shaft of a homogeneous reactor, overturning at a speed of 60 rpm, setting the temperature to 170 ℃, and treating the treatment time to 9 h. Cooling, filtering, collecting solid, washing with deionized water to neutrality, drying at 80deg.C overnight, and purifying to obtain precursor.
S3, spreading the 500 mg precursor at the bottom of the porcelain boat, placing the porcelain boat in a vacuum tube furnace, and placing the porcelain boat in N 2 Under the protection, the temperature is raised to 600 ℃ at the heating rate of 10 ℃/min, and the pyrolysis is carried out at constant temperature of 2 h. After cooling 264 mg Co@CN catalyst was obtained.
The Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer prepared in the embodiment is used for catalyzing the reaction of preparing 5-amino tetrahydroquinoline by selectively hydrogenating 5-amino quinoline. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 1 mmol 5-aminoquinoline, 50 mg Co@CN catalyst, 5 mL H 2 O, 3 MPa H 2 100 ℃, 6 h. The reactants and the products are determined by gas chromatography by an internal standard method, the conversion rate of 5-aminoquinoline is 84.7 percent, the selectivity of 5-aminotetrahydroquinoline is 100 percent, and the conversion rate of more than 80 percent and the selectivity of 100 percent can be still maintained after the catalyst is circulated for 10 times.
The above embodiments are only for illustrating the technical solution and features of the present invention, and are intended to be better implemented by those skilled in the art, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention are within the scope of the present invention, wherein the prior art is not specifically illustrated.

Claims (5)

1. The application of the Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer in the reaction of preparing tetrahydroquinoline compounds by selectively hydrogenating quinoline compounds is characterized in that the preparation method of the Co@CN catalyst derived from the nitrogen-containing super-crosslinked polymer comprises the following steps:
s1, dissolving a benzazepine heterocyclic compound, benzene, dimethoxymethane and anhydrous ferric trichloride in an organic solvent, heating to fully react, purifying and drying a resultant to obtain a nitrogen-containing super-crosslinked polymer;
s2, dispersing the polymer and cobalt salt into deionized water, adding urea, transferring to a reaction kettle, performing heat treatment under a turnover condition, cooling, separating, washing and drying to obtain a precursor;
s3, pyrolyzing the precursor in a nitrogen atmosphere to prepare a high-catalytic-activity nitrogen-containing super-crosslinked polymer-derived Co@CN catalyst;
the benzoazepine compound in S1 is selected from one or more of benzimidazole and benzotriazole; the adding molar ratio of the benzonitrogen heterocyclic compound to benzene is 1 (0.1-10); the molar ratio of the total amount of the benzazepine heterocyclic compound and benzene to the dimethoxymethane is 1 (1-4);
the heat treatment under the overturning condition in S2 is specifically as follows: and fixing the sealed high-pressure reaction kettle on a rotating shaft of the homogeneous phase reactor for overturning, wherein the rotating speed is 40-100 rpm, the temperature is 110-180 ℃, and the treatment time is 4-10 hours.
2. The use according to claim 1, wherein the organic solvent in S1 is selected from one or more of 1, 2-dichloroethane, dichloromethane, chloroform, carbon tetrachloride, cyclohexane.
3. The use according to claim 1, wherein the product in S1 is purified by the specific steps of: and carrying out Soxhlet extraction on the product for 10-24 hours by using methanol or ethanol.
4. The use according to claim 1, wherein the cobalt salt in S2 is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt sulphate.
5. Use according to claim 1, characterized in that the pyrolysis in S3 under nitrogen atmosphere is in particular: placing the precursor in a vacuum tube furnace, and adding the precursor into N 2 Under the protection, pyrolyzing 1-4 h in the temperature environment of 400-800 ℃.
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