CN109701574B - Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds - Google Patents
Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 71
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- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses preparation of a nitrogen-modified carbon-supported noble metal hydrogenation catalyst and hydrogenation reaction of pyridine ring compoundsThe use of (1). The preparation method comprises the following steps: 1) carrying out oxidation treatment on the activated carbon by using a treating agent, wherein the treating agent is perchloric acid, sodium chlorate or nitric acid, then placing the activated carbon treated by the treating agent in a flowing argon atmosphere, heating to 500-700 ℃, carrying out heat preservation treatment, and cooling to room temperature after the treatment is finished to obtain the pretreated activated carbon; 2) dissolving primary amine organic matters in water, adding pretreated active carbon, fully and uniformly mixing, and then placing in a hydrothermal kettle in a CO (carbon monoxide) environment2Carrying out hydrothermal reaction in the atmosphere to obtain nitrogen modified activated carbon; 3) and loading noble metal palladium and/or platinum on the nitrogen modified activated carbon by adopting an ultraviolet light reduction method to obtain the nitrogen modified carbon-loaded noble metal hydrogenation catalyst. The catalyst is applied to the catalytic hydrogenation reduction reaction of pyridine compounds, and has the characteristics of high conversion rate, good selectivity, good stability and high hydrogenation rate.
Description
(I) technical field
The invention relates to preparation and application of a hydrogenation catalyst, in particular to a preparation method of a nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of the nitrogen-modified carbon-supported noble metal hydrogenation catalyst in a catalytic hydrogenation reduction reaction of a pyridine ring compound.
(II) technical background
In the field of carbon-based materials, mesoporous/microporous carbon, carbon nanotubes, fullerenes, carbon aerogels, graphene, and the like have attracted considerable attention from researchers due to their unique structures and electronic properties. Of particular interest is the carbon element's own character and the hybrid structure of the carbon atom, including the atomic hybrid morphology (sp, sp)2And sp3) And heteroatom-doped carbon structures, the carbon materials can exhibit different morphologies, nanostructures, electronic properties, and chemical stability. For example, the carbon atom sp2The hybrid hexagonal lattice can show unique electronic effect, thermal effect and mechanical effect; sp2Bonded N (C)3Five-or six-membered ring structures of the structure or-NH-groups3N4Exhibit outstanding electronic, chemical and optical properties. As the adjacent elements of C, the N element and the C element have differences in atomic size, bond length and electronegativity, and the N element can introduce defects into the structure of the nano carbon material and adjust the electron distribution on carbon atoms. The introduction of N element into the carbon structure can effectively improve the characteristics of field emission, electron, photochemistry and the like. In recent years, carbon materials doped with heteroatoms (such as N, P, S and the like) are applied in the fields of energy conversion/storage devices, photovoltaic characteristics, adsorption/desorption, catalysis and the like.
There are two main methods for preparing nitrogen-doped nanocarbon materials, the first being an in-situ synthesis method, i.e., a method of in-situ synthesizing a nitrogen-doped carbon material by hydrothermal, polymerization or carbonization processes using an N-containing organic substance (simultaneously serving as a carbon source and a nitrogen source). Although the method can obtain the nitrogen-containing carbon material with high dispersion, the repeatability and the yield areA huge challenge. Yet another method of great interest compared to in situ synthesis is the subsequent synthesis, e.g., in a high temperature environment, of various carbon materials in a nitrogen-containing atmosphere (NH)3、N2Etc.) to form a nitrided carbon structure on the surface of the carbon material finally. The method enables the structural characteristics of the carbon material to be selected more, particularly the physical characteristics. Although mature and stable carbon materials can be selected as supports in this subsequent synthesis process, the harmful gases released during the treatment process of this nitriding process are still not environmentally friendly. Therefore, further research on a mild and effective nitrogen doping manner, a controllable nitrogen doping process and a nitrogen type is still a current research hotspot.
Disclosure of the invention
The first purpose of the invention is to provide a preparation method of a nitrogen-modified carbon-supported noble metal hydrogenation catalyst, which selectively generates a surface nitrogen structure with amino as a main part on the surface of active carbon, and the constructed active centers of noble metal and amino can effectively modify the electron cloud density and distribution of noble metal cluster particles, modulate the adsorption and desorption characteristics of reactants and product molecules in the hydrogenation reduction process and effectively promote the main reaction; and the preparation process is simple, convenient, efficient, economic, green and environment-friendly.
The second purpose of the invention is to provide the application of the nitrogen-modified carbon-supported noble metal hydrogenation catalyst in the catalytic hydrogenation reduction reaction of pyridine compounds, and the catalyst has the characteristics of high conversion rate, good selectivity, good stability and high hydrogenation rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a preparation method of a nitrogen-modified carbon-supported noble metal hydrogenation catalyst, which comprises the following steps:
1) normalization and selectivity treatment of carbon surface groups: taking activated carbon, wherein the surface of the activated carbon only contains CO2Leaving group (including carboxyl, anhydride, lactone) and CO2The total content of leaving groups is not higher than 0.8 mu mol/g, and the active carbon is treated with oxygen by using a treating agentPerforming chemical treatment, wherein the treating agent is perchloric acid, sodium chlorate or nitric acid, then placing the activated carbon treated by the treating agent in flowing argon atmosphere, heating to 500-700 ℃ for heat preservation treatment, cooling to room temperature after the treatment is completed, taking out a sample in the argon atmosphere, and sealing and storing to obtain the pretreated activated carbon; in the step, the surface of the activated carbon is oxidized and treated by a treating agent to enable the surface of the activated carbon to contain oxygen groups (including a CO leaving group and CO)2Leaving group) is significantly increased, and then CO is removed by high temperature treatment2A leaving group, leaving only the CO leaving group;
2) preparing nitrogen modified activated carbon by condensation reaction: dissolving a primary amine organic matter in water, adding the pretreated activated carbon, fully and uniformly mixing (preferably stirring and mixing for 0.5-2.0 hours), then placing the mixture in a hydrothermal kettle to perform hydrothermal reaction in the atmosphere of carbon dioxide, separating a sample after the reaction is completed, washing the sample to be neutral, and drying to obtain nitrogen modified activated carbon; in the step, a carbon monoxide leaving group and a primary amine group are subjected to condensation reaction under the hydrothermal condition of a carbon dioxide atmosphere to generate a surface nitrogen structure, wherein the surface nitrogen structure is mainly amino nitrogen;
3) noble metal loading: loading noble metal on the nitrogen modified activated carbon obtained in the step 2) by adopting an ultraviolet light reduction method, wherein the noble metal is palladium and/or platinum, and obtaining the nitrogen modified carbon-loaded noble metal hydrogenation catalyst.
In the invention, the activated carbon can be obtained by using a commercial product or treating the commercial product to obtain the activated carbon meeting the requirements. Preferably, the activated carbon particle size satisfies the following condition: the mass content of the particles between 200 and 300 meshes is not less than 80 percent. As a further preference, the specific surface area of the activated carbon is 850-1100m2G, ash content<3％。
Preferably, in the step 1), the activated carbon is treated by the following steps: uniformly dispersing the activated carbon into a treating agent solution with the concentration of 15-40 wt%, gradually heating the obtained suspension to 50-95 ℃ under stirring, continuously treating for 5-15h, and circularly condensing and absorbing tail gas by alkali liquor during the treatment; and then cooling the suspension to room temperature, carrying out suction filtration, washing with water until the pH value is neutral, and then drying.
As a further preference, the treating agent is sodium chlorate, which can enable the catalyst to obtain a faster hydrogenation reaction rate than other treating agents.
As a further preference, the volume dosage of the treating agent solution is 2-30mL/g calculated by the mass dosage of the activated carbon.
As a further preference, the drying conditions in step 1) are: vacuum drying at 80-120 deg.C for 3-5 hr.
Preferably, in the step 1), the activated carbon treated by the treating agent is heated to between 500 ℃ and 700 ℃ at the speed of 1-10 ℃/min, and the heat preservation treatment is carried out for 1-5 hours.
Preferably, in step 2), the primary amine-based organic substance contains at least two amine groups, and more preferably 1, 2-propanediamine, ethylenediamine or hexamethylenediamine.
Preferably, in the step 2), the feeding mass ratio of the primary amine organic matters to the pretreated activated carbon is 1-10: 1, the mass ratio of the amine organic matter to the water is 1: 1-10.
Preferably, in step 2), the hydrothermal reaction conditions are as follows: the temperature is 150 ℃ and 250 ℃, the time is 10-20h, and the pressure is 1.0-5.0MPa in the atmosphere of carbon dioxide.
Preferably, in step 2), the drying conditions are as follows: drying the mixture overnight at the temperature of 150 ℃ under the vacuum condition.
Preferably, the noble metal palladium and/or platinum in the step 3) is supported in an amount of 0.1 to 10 wt%.
Compared with other methods, the loading method has the advantages that the operation is simpler, the utilization rate of metal particles is high, and the morphology and the electronic structure (including the particle size and the proportion of each crystal face) of the noble metal can be more effectively controlled, so that the catalyst can meet different requirements of hydrogenation reaction. The invention specifically recommends that the ultraviolet light reduction method is implemented as follows: dispersing nitrogen modified activated carbon into water, dropwise adding a solution containing noble metal ions into the nitrogen modified activated carbon slurry under stirring, irradiating the nitrogen modified activated carbon slurry with ultraviolet light at room temperature for a certain time after the dropwise adding is finished, then continuously stirring for 0.5-2.0 hours, carrying out suction filtration, washing with water until the pH value is neutral, and drying to obtain the nitrogen modified carbon-supported noble metal hydrogenation catalyst. Preferably, the feeding mass ratio of the nitrogen modified activated carbon to the water is 1: 2-15. Preferably, the wavelength of the ultraviolet light is controlled to be 280-200nm, and the illumination time is controlled to be 5s-5 min. Preferably, the noble metal ion is in the form of a four-coordinate complex ion of a metal and chlorine. Preferably, the drying conditions are preferably: drying at 50-80 deg.C under vacuum overnight.
In the preparation process of the nitrogen modified carbon-supported noble metal hydrogenation catalyst prepared by the invention, the catalyst with the surface only containing CO is selected2The active carbon with leaving group is oxidized and treated at high temperature, so that the carbon surface only contains carbon monoxide leaving group (mainly ether, phenolic hydroxyl, carbonyl/quinone). These groups undergo condensation reaction with primary amine groups under hydrothermal conditions to generate a high-amino surface nitrogen structure (a typical hydrothermal reaction process is shown as the following formula, wherein the leftmost reactant is activated carbon containing a specific carbon monoxide leaving group, and the hydrothermal conditions are 200 ℃ and 12h as examples); noble metal ions are used as a noble metal source, and the noble metal is deposited in a nitrogen-rich center under the irradiation of ultraviolet light, so that the interaction between the noble metal and nitrogen is generated, the electron cloud density and distribution of noble metal cluster particles are effectively modified, the absorption and desorption characteristics of reactants and products in the hydrogenation reduction process are modulated, and the main reaction is effectively promoted.
On the other hand, the invention provides an application of the nitrogen-modified carbon-supported noble metal hydrogenation catalyst in catalyzing hydrogenation of pyridine ring compounds to synthesize piperidine compounds, wherein the application specifically comprises the following steps: and putting the pyridine ring compound and the nitrogen-modified carbon-supported noble metal hydrogenation catalyst into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air, filling hydrogen, starting stirring, and carrying out catalytic hydrogenation reaction at the temperature of 20-60 ℃ and the hydrogen pressure of 0.1-1.0MPa to obtain the piperidine compound. During the reaction, real-time sampling, filtering and separating, and analyzing the product by GC.
Preferably, in the application, the feeding mass ratio of the pyridine ring compound to the nitrogen-modified carbon-supported noble metal hydrogenation catalyst is 500: 0.1 to 4, more preferably 500: 0.2-2.0.
Preferably, in the application, the reaction temperature is 35-50 ℃, and the hydrogen pressure is 0.2-1.0 MPa.
The pyridine ring compound can be subjected to hydrogenation reaction in a solvent, and the suitable solvent is one or a mixed solvent of more than two of methanol, ethanol and DMF in any proportion. The volume dosage of the solvent is recommended to be 0.5-2.0mL/g based on the mass of the pyridine ring compound.
The pyridine ring compound can also be subjected to hydrogenation reaction under the solvent-free condition. When the solvent-free hydrogenation reaction is carried out, the raw materials are preheated and melted to be in a liquid state, and then the temperature is raised to the reaction temperature for the hydrogenation reaction.
When the batch hydrogenation reaction is carried out in the reaction kettle, the post-treatment method of the hydrogenation liquid comprises the following steps: filtering the hydrogenation liquid to separate out the catalyst, and distilling and dehydrating the organic phase to obtain the piperidine compound; the catalyst obtained by filtering can be returned to the reaction kettle for catalyst recycling. When continuous hydrogenation reaction is carried out in a fluidized bed or a reaction kettle, gas phase is pressurized and returned to a gas inlet system after gas-liquid separation, so that hydrogen circulation is realized; and intercepting catalyst particles in a solid-liquid phase in the reactor through a built-in filter of the reactor, wherein the liquid phase is similar to filtrate in the reaction kettle, and sequentially carrying out subsequent treatment methods to obtain the product piperidine compound.
The catalyst is particularly suitable for catalyzing a compound containing a pyridine ring and a benzyl group to perform coupling hydrogenation reaction of pyridine ring hydrogenation and hydrogenation debenzylation, in particular to a reaction for synthesizing 2, 3-piperidine dicarboximide by catalyzing and hydrogenating N-benzyl-2, 3-pyridine dicarboximide.
The catalyst of the invention, when the active carbon particle size as the raw material of the catalyst meets the following conditions: the mass content of the particles between 200 and 300 meshes is not less than 80 percent, and the catalyst is particularly suitable for a microchannel reactor.
Compared with the prior art, the invention has the beneficial effects that:
1) the method for modifying carbon by nitrogen is induced by a CO leaving group on the surface of carbon, and is driven by the condensation reaction of an amino group and the CO leaving group, so that a surface nitrogen structure mainly comprising amino is selectively generated. Compared with the existing synthetic method of the nitrogen carbon material, the method can regulate and control the type and the quantity of the required nitrogen structures, has very green and environment-friendly process, and is simple, convenient, economic and efficient to prepare. In addition, the constructed active centers of metal and amino can effectively modify the electron cloud density and distribution of noble metal cluster particles, and modulate the adsorption and desorption characteristics of reactant and product molecules in the hydrogenation reduction process, which is the main reason of the catalyst for generating higher coupling hydrogenation reaction activity of pyridine ring hydrogenation and hydrogenation debenzylation.
2) According to the preparation method of the nitrogen-modified carbon noble metal hydrogenation catalyst, the ultraviolet light is adopted to promote the photocatalytic reduction of metal ions in the nitrogen-rich center, so that the unique morphology structure and electronic structure of metal particles are formed, and the utilization rate of the metal particles is high.
3) The noble metal and amino active centers constructed in the catalyst can effectively modify the electron cloud density and distribution of noble metal cluster particles, and modulate the absorption and desorption characteristics of pyridine and piperidine molecules in the hydrogenation reduction process, which is the main reason for the catalyst to generate higher coupling hydrogenation reaction activity of pyridine ring hydrogenation and hydrogenation debenzylation. Specifically, the catalyst is used for synthesizing the piperidine compound by a catalytic hydrogenation method, the conversion rate is 100%, the selectivity can reach 100%, the stability is good, the consumption of the catalyst per ton of the piperidine compound is lower than 5g, and the hydrogenation rate is higher.
(IV) description of the drawings
FIG. 1 is a TEM image of the catalyst obtained in example 15.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
the activated carbon used in the examples of the present invention was Arkema CECA, France, and the structural parameters are shown in tables 1 and 2.
Examples 1 to 8: pretreatment of activated carbon
Uniformly dispersing 1.0g of activated carbon into 25.0mL of treating agent solution, placing the suspension in a 50mL round-bottom flask, gradually heating to 80 ℃ under constant-temperature heating and continuous stirring by a magnetic stirrer, keeping the temperature for 10 hours, and cyclically condensing and absorbing tail gas by alkali liquor in the period. And then, cooling the suspension to room temperature, carrying out suction filtration, washing with deionized water for multiple times until the pH value is neutral, and then placing in a vacuum oven to dry for 5 hours at 110 ℃.
And (3) placing part of the pretreated activated carbon sample in a flowing argon atmosphere, gradually heating to 800 ℃ from room temperature at the speed of 10 ℃/min, keeping the temperature at the target temperature for 2 hours, then gradually reducing to room temperature, taking out the sample in the argon atmosphere, and sealing and storing.
The samples obtained were obtained from the following references ((a) J.L.Figuerredo, M.F.R.Pereira, M.M.A.Fretias, J.J.M.Orfao, Carbon 1999,37, 1379-.
M.F.R.Pereira,J.J.M.
J.L.Figueiredo,J.L.Faria,P.Serp,Carbon 2008,46,1194-1207；(e)K.Friedel Ortega,R.Arrigo,B.Frank,R.
Trunscake, Chemistry of materials 2016,28, 6826-; (h) the types and contents of surface oxygen-containing groups were obtained by the methods reported in S.Wu, G.Wen, B.Zhong, B.Zhang, X.Gu, N.Wang, D.Su, Chinese J Catal 2014,35, 914-:
TABLE 1 physical structural Properties of raw carbon
Table 5.1 The effect of surface oxidantion on the physical structure of activated carbon.
TABLE 2 Effect of pretreatment on the type and content (. mu.mol) of surface groups on activated carbon
Example 10
1) Normalized selective treatment of carbon surface groups
1.0g of activated carbon is uniformly dispersed into 25.0mL of 30 wt% sodium chlorate solution, the suspension is placed into a 50mL round-bottom flask, the temperature is gradually raised to 95 ℃ under the continuous stirring of a constant-temperature heating magnetic stirrer for 5 hours, and the tail gas is circularly condensed and absorbed by alkali liquor in the period. And then, cooling the suspension to room temperature, carrying out suction filtration, washing with deionized water for multiple times until the pH value is neutral, and then placing in a vacuum oven to dry for 5 hours at 120 ℃.
And (3) placing the pretreated activated carbon sample in a flowing argon atmosphere, gradually heating the sample to 600 ℃ from room temperature at the speed of 10 ℃/min, keeping the temperature at the target temperature for 5 hours, then gradually cooling the sample to room temperature, taking out the sample in the argon atmosphere, and sealing and storing the sample.
2) Condensation reaction for preparing nitrogen modified carbon
Dissolving 10g of hexamethylenediamine in 30mL of deionized water, gradually adding 1.0g of the activated carbon obtained in the step 1) while stirring, transferring the mixture to a 50mL stainless steel hot kettle after magnetic stirring for 1h, placing the kettle in an oven, and performing CO treatment at 250 ℃ in a CO (carbon monoxide) system2Keeping the temperature of 5.0MPa for 10h, cooling the hydrothermal kettle to room temperature, taking out the lining, filtering the obtained sample, and washing with deionized waterThe mixture is dried overnight at 110 ℃ under vacuum condition until the pH value is neutral.
3) Metal ion load
Dispersing 1.0g of nitrogen modified carbon into 15mL of deionized water, dropwise adding 4.0mL of platinum and chlorine complex ion solution (platinum content is 0.005g/mL) into the nitrogen modified carbon slurry under the magnetic stirring state, irradiating by 200nm ultraviolet light for 5S after dropwise adding, then continuing to stir magnetically at normal temperature for 2h, carrying out suction filtration, washing until the pH value is neutral, and carrying out vacuum drying at 80 ℃ overnight to obtain the nitrogen modified carbon-supported noble metal hydrogenation catalyst.
Examples 11 to 24 are catalysts prepared according to the procedure of example 10, the specific variables parameters are shown in table 3.
Comparative example 1
The preparation method of the conventional carbon-supported palladium catalyst comprises the following steps: the specific surface area is 1100m2Drying and dehydrating activated carbon/g with the pore volume of 0.80mL/g for 4 hours at 110 ℃ in vacuum; transferring 10mL of chloropalladate solution with the concentration of 0.05g/mL into 50mL of deionized water, and adjusting the pH value of the chloropalladate solution to be 0.8 by using hydrochloric acid; then 10g of active carbon which is dried and dehydrated in vacuum is soaked in palladium liquid, fully stirred and soaked for 6 hours at 80 ℃, and the pH value is adjusted to 8-10 by 5 wt% of sodium hydroxide solution; after 1 hour, 2.5mL of hydrazine hydrate was added dropwise and reduced at 35 ℃ for 2 hours. Then cooling to room temperature, filtering the reaction system, washing the filter cake to be neutral by using deionized water, and drying and dehydrating for 4 hours at 110 ℃ to obtain the elemental palladium supported catalyst.
Comparative example 2
The procedure of example 10 was repeated except that the UV light was not used.
Comparative example 3
A high-temperature pretreatment step of removing activated carbon, namely, directly carrying out a condensation reaction on the activated carbon subjected to the oxidation treatment by using a 30 wt% nitric acid solution to prepare nitrogen-modified activated carbon, and the rest is the same as in example 10.
Comparative example 4
The raw carbon was directly subjected to the step 2) without pretreatment to prepare nitrogen-modified activated carbon, as in example 10.
Comparative example 5
The hydrothermal atmosphere was air, as in example 10.
Comparative example 6
The hydrothermal atmosphere was nitrogen, as in example 10.
Comparative example 7
The reduction process was carried out by UV irradiation at 350nm, as in example 10.
Examples 25 to 46 are examples in which the catalyst prepared by the above-mentioned preparation method is applied to the synthesis of piperidine compounds by catalytic hydrogenation of pyridine ring compounds.
Example 25
100g of N-benzyl-2, 3-pyridinedicarboximide and 0.1g of the catalyst of example 10 were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced with nitrogen, the nitrogen was replaced with hydrogen, the stirring was started, the number of stirring revolutions was 1400r/min, the reaction temperature was maintained at 50 ℃ and the hydrogen pressure was 1.0 MPa. Sampling, detecting the content of N-benzyl-2, 3-pyridine dicarboximide to be 0 by chromatography, stopping reaction, and filtering the catalyst. The filtrate is separated, dehydrated and distilled under reduced pressure to obtain the product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain the hydrogenation reaction with the conversion rate of 100 percent and the selectivity of 100 percent. The reaction time was 25 min.
Example 26
100g N-benzyl-3, 4-pyridinedicarboximide and 0.06g of the catalyst from example 11 were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced with nitrogen, the nitrogen was replaced with hydrogen, the stirring was started, the number of stirring revolutions was 1400r/min, the reaction temperature was maintained at 50 ℃ and the hydrogen pressure was 0.5 MPa. Sampling, and when the content of the N-benzyl-3, 4-pyridine dicarboximide is 0 by chromatographic detection, stopping the reaction, and filtering the catalyst. The filtrate is separated, dehydrated and distilled under reduced pressure to obtain the product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain the hydrogenation reaction with the conversion rate of 100 percent and the selectivity of 100 percent. The reaction time was 30 min.
Example 27
100g N-benzyl-3, 4-pyridinedicarboximide, 0.04g of the catalyst from example 15 and 100mL of methanol were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced with nitrogen, the nitrogen was replaced with hydrogen, the stirring was started, the stirring was carried out at 1400r/min, the reaction temperature was maintained at 35 ℃ and the hydrogen pressure was maintained at 0.5 MPa. Sampling, and when the content of the N-benzyl-3, 4-pyridine dicarboximide is 0 by chromatographic detection, stopping the reaction, and filtering the catalyst. The filtrate is separated, dehydrated and distilled under reduced pressure to obtain the product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain the hydrogenation reaction with the conversion rate of 100 percent and the selectivity of 100 percent. The reaction time was 20 min.
Example 28
100g N-benzyl-2, 3-pyridinedicarboximide and 0.1g of the catalyst from example 16 were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced with nitrogen, the nitrogen was replaced with hydrogen, the stirring was started, the number of stirring revolutions was 1400r/min, the reaction temperature was maintained at 35 ℃ and the hydrogen pressure was 0.5 MPa. Sampling, detecting the content of N-benzyl-2, 3-pyridine dicarboximide to be 0 by chromatography, stopping reaction, and filtering the catalyst. The filtrate is separated, dehydrated and distilled under reduced pressure to obtain the product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain the hydrogenation reaction with the conversion rate of 100 percent and the selectivity of 100 percent. The reaction time was 30 min.
Example 29
100g N-benzyl-2, 3-pyridinedicarboximide and 0.1g of the catalyst from example 18 were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced by nitrogen, the nitrogen was replaced by hydrogen, the stirring was started, the number of stirring revolutions was 1400r/min, the reaction temperature was maintained at 50 ℃ and the hydrogen pressure was 0.5 MPa. Sampling, detecting the content of N-benzyl-2, 3-pyridine dicarboximide to be 0 by chromatography, stopping reaction, and filtering the catalyst. The filtrate is separated, dehydrated and distilled under reduced pressure to obtain the product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain the hydrogenation reaction with the conversion rate of 100 percent and the selectivity of 100 percent. The reaction time was 25 min.
Example 30
100g N-benzyl-2, 3-pyridinedicarboximide and 0.1g of the catalyst from example 12 were placed in a 500mL autoclave, the autoclave was closed, the air in the reactor was replaced with nitrogen, the nitrogen was replaced with hydrogen, the stirring was started, the number of stirring revolutions was 1400r/min, the reaction temperature was maintained at 50 ℃ and the hydrogen pressure was 0.5 MPa. The reaction kettle is a continuous kettle type reactor, and the catalyst is ensured to be remained in a reaction system through an online filtering device. On-line sampling, and adjusting the feeding amount under the condition that the content of N-benzyl-2, 3-pyridine dicarboximide is 0 through chromatographic detection. The obtained filtrate is subjected to phase separation and water separation and reduced pressure distillation dehydration to obtain a product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain a hydrogenation reaction conversion rate of 100% and a selectivity of 100%. The reaction is stably operated for more than 1000h, and the discharging amount is more than 200 kg.
Example 31
100g N-benzyl-2, 3-pyridinedicarboximide and 0.1g of the catalyst from example 19 were placed in a 500mL fluidized-bed reactor, the air in the reactor was replaced by nitrogen, then hydrogen was used to replace nitrogen, stirring was started at 1400r/min, the reaction temperature was maintained at 50 ℃ and the hydrogen pressure was 0.5MPa, and the reaction was carried out. The reactor is a fluidized bed reactor, and the catalyst is ensured to be remained in a reaction system through an online filtering device. On-line sampling, and adjusting the feeding amount under the condition that the content of N-benzyl-2, 3-pyridine dicarboximide is 0 through chromatographic detection. The obtained filtrate is subjected to phase separation and water separation and reduced pressure distillation dehydration to obtain a product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain a hydrogenation reaction conversion rate of 100% and a selectivity of 100%. The reaction is stably operated for more than 1000h, and the discharging amount is more than 300 kg.
Example 32
100g N-benzyl-2, 3-pyridinedicarboximide, 0.1g of the catalyst of example 20 and 120ml of water were charged into a microchannel reactor from Corning, and the reaction was started by displacing the air in the reactor with nitrogen and then displacing the nitrogen with hydrogen. The reaction temperature was maintained at 50 ℃ and the hydrogen pressure at 0.8 MPa. The catalyst is ensured to be remained in the reaction system through an online filtering device. On-line sampling, and adjusting the feeding amount under the condition that the content of N-benzyl-2, 3-pyridine dicarboximide is 0 through chromatographic detection. The obtained filtrate is subjected to phase separation and water separation and reduced pressure distillation dehydration to obtain a product, and the product is subjected to chromatographic quantitative analysis (molar percentage) to obtain a hydrogenation reaction conversion rate of 100% and a selectivity of 100%. The reaction is stably operated for more than 2000h, and more than 400 kg of materials are discharged.
Examples 33 to 46
Referring to example 25, the catalyst was changed and the results are shown in table 4.
TABLE 4 catalytic Performance results for examples 11-24 at the reaction conditions of example 25
Comparative examples 8 to 15
Comparative examples 1-7 the performance of the catalysts tested under the conditions of example 27 and the results are shown in table 5.
TABLE 5 catalytic Performance of comparative examples 1-7 under the reaction conditions of example 27
TABLE 6 results of the experiment for applying the catalyst of example 27
Table 7 catalyst prepared in example 15 with nitrogen species content and bond energy
Note: n is a radical ofPD: pyridine nitrogen; n is a radical ofA: an amino nitrogen; n is a radical ofPR: pyrrole nitrogen; n is a radical ofQ: quaternary ammonium nitrogen.
Claims (11)
1. A preparation method of a nitrogen-modified carbon-supported noble metal hydrogenation catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
1) normalization and selectivity treatment of carbon surface groups: taking activated carbon, wherein the surface of the activated carbon only contains CO2Leaving group and CO2The total content of leaving groups is not higher than 0.8 mu mol/g, and the activated carbon is oxidized by a treating agent, and the treating agent is specifically used for treating the activated carbon by the following steps: uniformly dispersing activated carbon into a treating agent solution with the concentration of 15-40 wt%, gradually heating the obtained suspension to 50-95 ℃ under stirring, continuously treating for 5-15h, circularly condensing and absorbing tail gas by alkali liquor during the period, cooling the suspension to room temperature, performing suction filtration, washing with water until the pH value is neutral, and then drying; the treating agent is perchloric acid, sodium chlorate or nitric acid, then the activated carbon treated by the treating agent is placed in flowing argon atmosphere, the temperature is raised to 500-700 ℃ for heat preservation treatment, the temperature is reduced to room temperature after the treatment is finished, and a sample is taken out and sealed and stored in the argon atmosphere to obtain the pretreated activated carbon;
2) preparing nitrogen modified activated carbon by condensation reaction: dissolving primary amine organic matters in water, adding pretreated active carbon, fully and uniformly mixing, and then placing in a hydrothermal kettle to perform hydrothermal reaction in carbon dioxide atmosphere, wherein the hydrothermal reaction conditions are as follows: the temperature is 150 ℃ and 250 ℃, the time is 10-20h, the atmosphere of carbon dioxide and the air pressure is 1.0-5.0MPa, the sample is separated after the reaction is completed, the sample is washed to be neutral and dried, and the nitrogen modified activated carbon is obtained;
3) noble metal loading: loading noble metal on the nitrogen modified activated carbon obtained in the step 2) by adopting an ultraviolet light reduction method, wherein the noble metal is palladium and/or platinum, and obtaining the nitrogen modified carbon-loaded noble metal hydrogenation catalyst.
2. The method of claim 1, wherein: the activated carbon particle size satisfies the following conditions: the mass content of the particles between 200 and 300 meshes is not less than 80 percent.
3. The method of claim 1 or 2, wherein: in the step 1), the volume dosage of the treating agent solution is 2-30mL/g calculated by the mass dosage of the activated carbon, and the drying condition is as follows: vacuum drying at 80-120 deg.C for 3-5 hr; heating the activated carbon treated by the treating agent to between 500 ℃ and 700 ℃ at the speed of 1-10 ℃/min, and carrying out heat preservation treatment for 1-5 hours.
4. The method of claim 1 or 2, wherein: in the step 2), the primary amine organic matter at least contains two amino groups; the feeding mass ratio of the primary amine organic matters to the pretreated activated carbon is 1-10: 1, the mass ratio of the primary amine organic matter to the water is 1: 1-10.
5. The method of claim 4, wherein: in the step 2), the primary amine organic matter is 1, 2-propane diamine, ethylene diamine or hexamethylene diamine.
6. The method of claim 1 or 2, wherein: in the step 3), the loading amount of the noble metal palladium and/or platinum is 0.1-10 wt%.
7. The method of claim 1 or 2, wherein: the ultraviolet light reduction method is implemented as follows: dispersing nitrogen modified activated carbon into water, dropwise adding a solution containing noble metal ions into the nitrogen modified activated carbon slurry under stirring, irradiating ultraviolet at room temperature for a certain time after dropwise adding, controlling the wavelength of the ultraviolet to be 280-5 min, controlling the irradiation time to be 5s-5min, then continuously stirring for 0.5-2.0 h, carrying out suction filtration, washing until the pH value is neutral, and drying to obtain the nitrogen modified carbon-supported noble metal hydrogenation catalyst.
8. The application of the nitrogen-modified carbon-supported noble metal hydrogenation catalyst prepared by the preparation method of claim 1 in catalyzing hydrogenation of pyridine ring compounds to synthesize piperidine compounds, specifically: putting a pyridine ring compound and the nitrogen-modified carbon-supported noble metal hydrogenation catalyst into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air, filling hydrogen, starting stirring, and carrying out catalytic hydrogenation reaction at the temperature of 20-60 ℃ and the hydrogen pressure of 0.1-1.0MPa to obtain a piperidine compound; the catalytic hydrogenation reaction is carried out in a solvent or under the condition of no solvent, and the solvent is one or a mixed solvent of more than two of methanol, ethanol and DMF in any proportion.
9. The use of claim 8, wherein: the pyridine ring compound is a compound containing a pyridine ring and a benzyl, and the coupling hydrogenation reaction of pyridine ring hydrogenation and hydrogenation debenzylation is carried out in the hydrogenation reaction process.
10. The use of claim 9, wherein: the nitrogen-modified carbon-supported noble metal hydrogenation catalyst is applied to the reaction of synthesizing 2, 3-piperidine dicarboximide by catalytic hydrogenation of N-benzyl-2, 3-pyridine dicarboximide.
11. Use according to any one of claims 8 to 10, wherein: when the particle size of the activated carbon as the catalyst raw material satisfies the following condition: the mass content of the particles between 200 and 300 meshes is not less than 80 percent, and the catalyst is applied to a microchannel reactor.
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