CN110302769B - Catalyst carrier, supported catalyst, preparation method and application thereof - Google Patents

Catalyst carrier, supported catalyst, preparation method and application thereof Download PDF

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CN110302769B
CN110302769B CN201810227799.6A CN201810227799A CN110302769B CN 110302769 B CN110302769 B CN 110302769B CN 201810227799 A CN201810227799 A CN 201810227799A CN 110302769 B CN110302769 B CN 110302769B
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catalyst
carrier
boron
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reaction
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CN110302769A (en
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潘秀莲
铁锴
包信和
李攀
何丽敏
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Dalian Institute of Chemical Physics of CAS
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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Abstract

The invention relates to a catalyst carrier, a supported catalyst, a preparation method and application thereof, and mainly solves the problems that the interaction force between a carbon material and supported metal nanoparticles is weak, and the metal nanoparticles are easy to aggregate, grow and fall off in the heterogeneous catalytic reaction process. The invention adopts biomass sugar and boron-containing compound as precursors, and prepares the boron-doped carbon material by high-temperature roasting, thereby better solving the problems. The doped carbon material and the metal nanoparticles have strong interaction, and when the doped carbon material is used as a carrier to load the metal nanoparticles, the metal nanoparticles can be uniformly dispersed, the aggregation and falling off of the metal nanoparticles in the catalytic reaction process can be effectively inhibited, and the activity and stability of the catalyst can be obviously improved. The doped carbon material has the advantages of wide raw material source, low price, easy obtainment and simple preparation process, and has good application prospect as an ideal metal nanoparticle carrier material.

Description

Catalyst carrier, supported catalyst, preparation method and application thereof
Technical Field
The invention relates to a catalyst carrier, a supported catalyst, a preparation method and application thereof.
Background
Compared with a non-supported metal catalyst, the supported metal catalyst has the characteristics of greatly improving the activity of the catalyst, improving the selectivity of the catalyst, reducing the cost of the catalyst, easily separating the catalyst from a reaction product, easily recycling an active component and the like, and is widely applied to the aspects of petrochemical industry, energy conversion, environmental protection and the like. Commonly used catalyst supports include: metal oxide carriers, carbon material carriers, molecular sieve carriers, and natural substances such as zeolite, diatomaceous earth, and the like. Among them, carbon materials have been one of the earliest materials used as a metal catalyst support because of their advantages such as a developed pore structure, a high specific surface area, excellent acid and alkali resistance, a high thermal conductivity, and low cost, and have been receiving much attention.
The activity and stability of the catalyst are two important indicators used to evaluate the performance of the catalyst. It is well known that the activity of a catalyst is closely related to factors such as the specific surface area, the geometric configuration and the like of its active components. In the supported metal catalyst, since the metal is dispersed on the carrier, the lattice defect of the metal is increased and new active sites are generated while the active surface area of the metal component is increased, and thus the supported metal catalyst has high reaction activity. However, under the influence of the inert surface of the carbon carrier, the interaction between the metal active component and the carrier is weak, and under some harsh reaction conditions, the metal particles are easy to aggregate and grow up and fall off from the carrier, so that the reaction activity of the catalyst is reduced. Therefore, it is important to enhance the interaction between the metal active component and the carbon support to improve the stability of the catalyst. At present, there are various methods for improving the surface chemical activity of carbon materials, and among these, the method of doping with hetero atoms is most widely used. The heteroatom doping can effectively improve the electrical property and the physical and chemical properties of the carbon carrier, and a large number of defect sites can be introduced on the surface of the carbon carrier in the doping process, thereby being beneficial to the deposition of metal particles and the enhancement of the interaction between metal and the carrier.
Nitrogen doped carbon materials have been the focus of research by scientists in recent years. Also as the boron atom closest to the carbon atom in the periodic table, although theoretical calculations show that boron atoms enhance the interaction between the metal particles and the carrier more effectively than nitrogen atoms, they are far from nitrogen atoms in practical systems. The highly toxic boron-containing precursors used during the preparation of boron-doped carbon materials and the excessively high processing temperatures are one of the reasons why their research is inhibited. At present, highly toxic precursors such as benzene trichloride, triethylborane and the like are usually used for preparing the boron-doped carbon material, the reaction temperature is 900 ℃ or above, and the preparation process of using a small amount of boric acid as the precursor usually needs to be carried out for long-time doping at 1000 ℃ or even higher. It is reported in the literature that boron is doped with boric acid at 900 ℃ for 3 hours in an amount of only 0.2 at.%, and with 4-hydroxyphenylboronic acid at 900 ℃ in an amount of only 1.3 at.%. Therefore, the boron-doped carbon material is prepared by using a non-toxic or low-toxicity boron-containing precursor and a milder treatment temperature, a higher boron doping amount is ensured, and the boron-doped carbon material is used as a carrier to enhance the interaction between metal particles and a carbon carrier, so that the service life of the catalyst is prolonged, and the boron-doped carbon material has important significance for basic research and industrial application.
Disclosure of Invention
The purpose of the invention is: the method for preparing the boron-doped carbon material simply is provided, and the prepared material is used as a carrier of the metal nanoparticles, so that the problems that the interaction force between the carbon material and the loaded metal nanoparticles is weak, and the metal nanoparticles are easy to aggregate and fall off in heterogeneous catalytic reaction are solved. The invention uses biomass sugar and non-toxic or low-toxicity boron-containing compound as precursors, the preparation conditions are mild, the preparation method is simple, and the product can effectively enhance the interaction between the carbon carrier and the loaded metal.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a catalyst carrier is an amorphous carbon material modified with boron and oxygen, the amorphous carbon material has a flaky porous structure, and the specific surface area of the catalyst carrier is 800-1800m2G, preferably 1000-1700m2Per g, total pore volume of 0.4-1.0cm3In g, preferably from 0.5 to 0.8cm3The volume of the micropores accounts for 60-80% of the total volume.
As a preferable technical scheme, the boron element and the oxygen element form a bond with the carbon element in a covalent bond mode; the boron element and the carbon element form BC3、BCO2、BC2O、B4At least one of C structure is doped in the carbon material skeleton; the oxygen element and the carbon element form at least one of an ether oxygen structure, a quinone oxygen structure and a hydroxyl oxygen structure, and the oxygen element and the carbon element are doped in the carbon material skeleton.
As a preferable technical scheme, the content of the carbon element is 80-95%, preferably 85-90%, the content of the boron is 0.5-7%, preferably 1.5-3%, and the content of the oxygen element is 5-18%, preferably 8-13%, in percentage by weight of the catalyst carrier.
The invention also provides a preparation method of the catalyst carrier, which comprises the steps of fully mixing the aqueous solution containing the carbon source and the boron source, pre-drying, and then roasting at high temperature for carbonization treatment.
The method preferably comprises the steps of:
a) dissolving a carbon source and a boron source in water to obtain a solution 1, and stirring at room temperature for 8-24 h;
b) continuously stirring the solution 1 at the temperature of 50-80 ℃ to dry the solution to obtain a solid 1;
c) transferring the solid 1 to a tubular furnace, roasting for 1-3h at the temperature of 200-400 ℃ in an inert atmosphere, and then heating to the temperature of 600-1200 ℃ for roasting for 1-6h to obtain a product;
d) after naturally cooling to room temperature, grinding the product;
e) and washing and drying the ground product to obtain the catalyst carrier.
In a preferred embodiment, the carbon source is a biomass sugar, preferably at least one of glucose, fructose, sucrose, xylose, starch, and cellulose, and more preferably at least one of glucose, sucrose, and cellulose; the boron source is at least one of boric acid, boron trioxide, elemental boron and sodium tetraborate, preferably at least one of boric acid and boron trioxide.
As a preferred technical scheme, in the step a), the carbon source and the boron source are used in an amount such that the molar ratio of C to B in the solution 1 is 6:5-6:0.5, preferably 3:1-6: 1.
As a preferable technical scheme, in the step c), the inert atmosphere is at least one of argon, nitrogen and helium, preferably argon, and the gas flow rate is 50-150ml/min, preferably 100-120 ml/min; the roasting process is divided into two steps, firstly roasting for 1-3h at the temperature of 200-400 ℃ in an inert atmosphere, preferably for 1-1.5h at the temperature of 250-300 ℃, and then roasting for 1-6h at the temperature of 600-1200 ℃, preferably for 1000-4 h at the temperature of 800-1000 ℃.
As a preferable technical solution, in the step e), at least one of hot water, ethanol and methanol, preferably hot water with a temperature of 100-.
The invention also provides a supported catalyst, which comprises a carrier and an active component, wherein the carrier is any one of the catalyst carriers, and the active component is metal.
Preferably, the metal is at least one of palladium, platinum, ruthenium, rhodium, cobalt, nickel, iridium and osmium, and the metal loading is 0.2wt% to 5.0wt%, preferably 0.5 wt% to 1.0 wt%.
The invention also provides a preparation method of the supported catalyst, which is characterized in that the catalyst carrier is impregnated by adopting a soluble metal salt solution, wherein the soluble metal salt solution is at least one of chloride, nitrate and acetate solutions of palladium, platinum, ruthenium, rhodium, cobalt, nickel, iridium and osmium, and preferably at least one of chloride solutions of palladium, platinum, ruthenium and rhodium.
The invention also provides the application of the supported catalyst, and the supported catalyst is used in a fixed bed, a trickle bed or a kettle type reactor for catalytic hydrogenation, oxidation, disproportionation and coupling reaction.
The invention also provides a method for hydrogenating p-carboxybenzaldehyde, which takes p-carboxybenzaldehyde as a raw material and water as a reaction solvent, and the raw material is contacted with the supported catalyst of claim 10 or 11 under the conditions that the reaction temperature is 80-280 ℃ and the hydrogen pressure is 0.1-8MPa to generate p-hydroxymethylbenzoic acid or p-toluic acid.
The invention also provides a method for oxidizing glucose, which takes glucose as a raw material, takes water and alkali solution with certain concentration as a reaction solvent, and contacts the raw material with the supported catalyst in the claim 10 or 11 under the conditions that the reaction temperature is 40-80 ℃ and the oxygen pressure is normal pressure to generate gluconate.
The invention also provides a Suzuki coupling method, which takes aryl halide and organic boric acid as raw materials, takes water or a mixture of the water and an organic solvent as a reaction solvent, adds a certain amount of alkali, and contacts the raw materials with the supported catalyst of claim 10 or 11 at the reaction temperature of 30-120 ℃ to generate aromatic hydrocarbon.
Analysis and test show that the prepared boron-doped carbon material, namely the catalyst carrier, has a flaky porous structure, and boron is BC3、BCO2、BC2O、B4One or more than one type of C structure is doped in the carbon material framework. The boron content is 0.5-7%, preferably 1.5-3%, by weight of the boron-doped carbon material. Analysis and test show that the specific surface area of the prepared boron-doped carbon material is 800-1800m2G, preferably 1000-1700m2Per g, total pore volume of 0.4-1.0cm3In g, preferably from 0.5 to 0.8cm3The content of micropores accounts for 60-80% of the total pore volume, and the content of mesopores accounts for 20-40% of the total pore volume.
The invention has the following advantages:
(1) the carbon source and the boron source related by the invention have wide sources, are cheap and easy to obtain, and reduce the manufacturing cost of the boron-doped carbon material;
(2) the carbon source related by the invention is nontoxic and harmless, is environment-friendly, and avoids damaging the environment;
(3) the preparation process is simple, the preparation conditions are mild, and the coordination effect between the carbon source and the boron source in the aqueous solution can effectively reduce the energy consumption in the subsequent roasting process;
(4) the doping amount of boron can be adjusted according to different requirements, and the preparation method is simple and feasible;
(5) the surface chemical activity of the carbon material is changed by boron doping, the interaction force between the carbon carrier and the loaded metal catalyst is enhanced, the metal nanoparticles can be uniformly dispersed, the aggregation and falling off of the metal nanoparticles in the catalytic reaction process are effectively inhibited, the stability of the catalyst is improved, and the service life of the catalyst is prolonged.
Drawings
Fig. 1 is a Transmission Electron Micrograph (TEM) of the catalyst support obtained in example 1.
Fig. 2 is a Raman spectrum (Raman) of the catalyst carrier obtained in example 1.
Fig. 3 is an X-ray photoelectron spectrum (XPS) of boron in the catalyst support obtained in example 1.
FIG. 4 is a High Resolution Transmission Electron Micrograph (HRTEM) of the supported catalyst obtained in example 1.
FIG. 5 is a High Resolution Transmission Electron Micrograph (HRTEM) of the supported catalyst obtained in example 1 after aging.
Fig. 6 is a high-resolution transmission electron micrograph (HRTEM) of the supported catalyst obtained in comparative example 1.
FIG. 7 is a High Resolution Transmission Electron Micrograph (HRTEM) of the supported catalyst obtained in comparative example 1 after aging.
Fig. 8 is a high-resolution transmission electron micrograph (HRTEM) of the supported catalyst obtained in comparative example 2.
Detailed Description
Dissolving biomass saccharide and boron-containing compound in water according to a certain proportion, stirring at room temperature for 8-24h, and continuously stirring at 50-80 ℃ until the mixture is dried; then roasting and drying the sample in an inert atmosphere, naturally cooling and grinding the product; and finally, washing and drying the ground product to obtain the boron-doped carbon material, namely the catalyst carrier.
And soaking the prepared boron-doped carbon material in a soluble metal salt solution, standing, drying, and then reducing in hydrogen to finally obtain the metal catalyst loaded with the boron-doped carbon material. The standing time is 4-24h, preferably 8-12 h. The reduction time is 1-6h, preferably 2-4h, ensuring complete reduction of the supported metal.
The invention is described in detail below with reference to the figures and the embodiments. The following examples are only illustrative of the present invention, and the scope of the present invention shall include the full contents of the claims, not limited to the examples.
Example 1
Preparing a carrier:
(1) 3.0g of glucose and 1.6g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) Transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow rate of 100mL/min, heating to 800 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow rate of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The TEM characterization yielded the morphology of the catalyst support, as shown in fig. 1, indicating that the support consists of a sheet-like structure. Raman results indicate that the catalyst support is composed of an amorphous carbon material, as shown in figure 2. XPS results show that boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton as shown in fig. 3. The ICP-OES results show that the boron content therein was 1.5% in weight percent of the catalyst support. The BET result shows that the obtained catalyst carrier has a rich hierarchical pore structure, and the specific surface area of the catalyst carrier is 1400.0m2Per g, total pore volume of 0.68cm3In which the micropore volume accounts for 69% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric soaking method, standing for 12h, drying, then placing in hydrogen for reduction at the hydrogen flow rate of 50mL/min and at 250 ℃ for 2 h.
The morphology of the obtained supported catalyst is characterized by HRTEM, as shown in fig. 4, wherein the palladium content is 0.5 wt.%, and the palladium particles are uniformly dispersed on the catalyst carrier and have a particle size between 0.5 and 3 nm.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 77.0%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging, 200mg of the raw material was added, and an activity test was performed under the same conditions as the fresh catalyst, and the conversion of the raw material was 60.4% after 40min of reaction. The morphology of the aged catalyst was characterized by HRTEM, as shown in fig. 5, it can be seen that the palladium particles were still very uniformly dispersed on the catalyst support. In addition, the ICP results show that there is no significant reduction in the palladium particle content of the catalyst after aging. The two points show that the prepared catalyst carrier has good stabilizing effect on palladium particles.
Example 2
Preparing a carrier:
(1) 3.0g of glucose and 3.2g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) And transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow rate of 100mL/min, heating to 900 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow rate of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content therein was 2.1% by weight of the catalyst support. The obtained catalyst carrier had a specific surface area of 1680.7m2Per g, total pore volume of 0.78cm3In which the micropore volume accounts for 76% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 2h at 250 ℃ to obtain the supported palladium catalyst with the palladium content of 0.5 wt.%.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 86.4%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging, 200mg of the raw material was added, and an activity test was performed under the same conditions as the fresh catalyst, and the conversion of the raw material was 72.6% after 40min of reaction. The palladium particles in the aged catalyst do not grow and run off obviously, which shows that the prepared catalyst carrier has good stabilizing effect on the palladium particles.
Example 3
Preparing a carrier:
(1) 3.0g of glucose and 3.2g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) And transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow speed of 100mL/min, heating to 1000 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the argon flow speed of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content therein was 2.3% by weight of the catalyst support. The obtained catalyst carrier had a specific surface area of 1586.3m2Per g, total pore volume of 0.72cm3In which the micropore volume accounts for 73% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 2h at 250 ℃ to obtain the supported palladium catalyst with the palladium content of 0.5 wt.%.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 89.3%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging, 200mg of the raw material was added, and an activity test was performed under the same conditions as the fresh catalyst, and the conversion of the raw material was 78.0% after 40min of reaction. The palladium particles in the aged catalyst do not grow and run off obviously, which shows that the prepared catalyst carrier has good stabilizing effect on the palladium particles.
Example 4
Preparing a carrier:
(1) 3.0g of glucose and 0.8g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) And transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow speed of 100mL/min, heating to 1000 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the argon flow speed of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier is made of a flaky indefinite material modified with boron and oxygenA type carbon material, wherein boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content therein was 0.92% by weight of the catalyst support. The obtained catalyst carrier had a specific surface area of 983.4m2Per g, total pore volume of 0.52cm3(ii)/g, wherein the micropore volume accounts for 63% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 2h at 250 ℃ to obtain the supported palladium catalyst with the palladium content of 0.5 wt.%.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 64.9%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging, 200mg of the raw material was added, and an activity test was performed under the same conditions as the fresh catalyst, and the conversion of the raw material was 42.5% after 40min of reaction. The palladium particles in the aged catalyst do not grow and run off obviously, which shows that the prepared catalyst carrier has good stabilizing effect on the palladium particles.
Example 5
Preparing a carrier:
(1) 3.0g of glucose and 1.6g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) Transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow rate of 100mL/min, heating to 800 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow rate of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content therein was 1.5% by weight of the catalyst support. The specific surface area of the obtained catalyst carrier is 1400.0m2Per g, total pore volume of 0.68cm3In which the micropore volume accounts for 69% of the total pore volume.
Preparing a catalyst:
soaking a dried catalyst carrier in hydrochloric acid aqueous solution of palladium chloride and ruthenium chloride by an isometric impregnation method, standing for 12h, adding 1mol/L sodium hydroxide solution, stirring for 30min, performing suction filtration, washing, drying and other processes, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing at 250 ℃ for 2h to obtain the supported palladium-ruthenium catalyst with the palladium content of 0.3 wt.% and the ruthenium content of 0.2 wt.%.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 54.7%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging, 200mg of the raw material was added, and an activity test was performed under the same conditions as for the fresh catalyst, and the conversion of the raw material was 46.4% after 40min of reaction. The palladium particles in the aged catalyst do not grow and run off obviously, which shows that the prepared catalyst carrier has good stabilizing effect on the palladium particles.
Example 6
Preparing a carrier:
(1) 3.0g of glucose and 1.6g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) Transferring the dried sample to a tube furnace, heating to 300 ℃ at the speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the speed of 120mL/min, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the speed of 120mL/min, and cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content was 1.7% by weight of the catalyst support. The obtained catalyst carrier had a specific surface area of 1298.6m2(g) total pore volume of 0.63cm3In which the micropore volume accounts for 77% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 2h at 250 ℃ to obtain the supported palladium catalyst with the palladium content of 1.0 wt.%.
Evaluation of glucose oxidation performance:
the catalyst catalyzes the glucose oxidation reaction to be carried out in a tank reactor with the volume of 100mL, the reaction is carried out at the temperature of 50 ℃, the oxygen pressure is normal pressure, the flow rate is 40mL/min, the stirring speed is 300rpm, the raw material addition amount is 5g, the catalyst addition amount is 50mg, and the water addition amount is 70 mL. Continuously dropwise adding 1mol/L sodium hydroxide solution in the reaction process, and keeping the pH value of the reaction system constant at 9. The reaction is carried out for 4 hours, the conversion rate of the raw materials is 86.9 percent, and the selectivity of the sodium gluconate is 84 percent.
Example 7
Preparing a carrier:
(1) 3.0g of glucose and 1.6g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) Transferring the dried sample to a tube furnace, heating to 300 ℃ at the speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the speed of 120mL/min, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, roasting for 2h at the speed of 120mL/min, and cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content was 1.7% by weight of the catalyst support. The obtained catalyst carrier had a specific surface area of 1298.6m2(g) total pore volume of 0.63cm3In which the micropore volume accounts for 77% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a platinum dichloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 3h at 350 ℃ to obtain the supported platinum catalyst with the platinum content of 1.0 wt.%.
Evaluation of glucose oxidation performance:
the catalyst catalyzes the glucose oxidation reaction to be carried out in a tank reactor with the volume of 100mL, the reaction is carried out at the temperature of 50 ℃, the oxygen pressure is normal pressure, the flow rate is 40mL/min, the stirring speed is 300rpm, the raw material addition amount is 5g, the catalyst addition amount is 50mg, and the water addition amount is 70 mL. Continuously dropwise adding 1mol/L sodium hydroxide solution in the reaction process, and keeping the pH value of the reaction system constant at 9. After 4 hours of reaction, the conversion rate of the raw material is 93.4 percent, and the selectivity of the sodium gluconate is 92 percent.
Example 8
Preparing a carrier:
(1) 3.0g of glucose and 3.2g of boric acid are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) And transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow speed of 100mL/min, heating to 900 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow speed of 100mL/min, and then cooling.
(4) Grinding the roasted product into fine powder in a mortar, washing the fine powder in a sand core funnel for three times by using hot water, washing the fine powder once by using absolute ethyl alcohol, and then putting the fine powder into an oven for drying to obtain the carrier.
The obtained catalyst carrier consists of a flaky amorphous carbon material modified with boron and oxygen, wherein the boron is BC3、BCO2And BC2The form of O is doped in the carbon material skeleton. The boron content therein was 2.1% by weight of the catalyst support. The specific surface area of the obtained catalyst carrier was 1624.8m2(g) total pore volume of 0.75cm3In which the micropore volume represents 74% of the total pore volume.
Preparing a catalyst:
soaking the dried catalyst carrier in a palladium chloride hydrochloric acid aqueous solution by an isometric impregnation method, standing for 12h, drying, then placing in hydrogen for reduction, wherein the hydrogen flow rate is 50mL/min, and reducing for 2h at 250 ℃ to obtain the supported palladium catalyst with the palladium content of 2.0 wt.%.
Evaluation of Suzuki coupling Performance:
the catalyst catalyzes Suzuki coupling reaction to be carried out in a tank reactor with the volume of 50mL, the reaction is carried out at 80 ℃, the stirring speed is 300rpm, the addition amount of bromobenzene is 4mmol, the addition amount of phenylboronic acid is 8mmol, the addition amount of catalyst is 40mg, the addition amount of water is 10mL, the addition amount of N, N-dimethylformamide is 30mL, and the addition amount of potassium carbonate is 2.0 g. The reaction was carried out for 4h, with a feed conversion of 92.4%. The catalyst is recycled for five times, and the activity of the catalyst is not obviously reduced, which shows that the prepared catalyst carrier has good stabilizing effect on palladium particles.
Comparative example 1
Preparing a carrier:
(1) weighing 3.0g of glucose, placing the glucose in a tube furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow rate of 100mL/min, heating to 800 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow rate of 100mL/min, and then cooling.
(2) The calcined product was ground into a fine powder in a mortar to obtain a carrier.
The resulting catalyst support consists of a sheet of amorphous carbon material. The BET result showed that the specific surface area of the obtained catalyst carrier was very small, only 80.7m2Per g, total pore volume of 0.08cm3(ii)/g, micropores are almost absent.
Preparing a catalyst:
soaking the catalyst carrier in palladium chloride hydrochloric acid aqueous solution by an isometric soaking method, standing for 12h, drying, then placing in hydrogen for reduction at the hydrogen flow rate of 50mL/min and at 250 ℃ for 2 h.
The morphology of the obtained supported catalyst was characterized by TEM, as shown in fig. 6, wherein the palladium content was 0.5 wt.%, the palladium particles were not uniformly dispersed on the catalyst support, and there were particles with large particle size.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 29.4%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging is finished, 200mg of raw material is added, and an activity test is carried out under the same condition with a fresh catalyst, the conversion rate of the raw material is only 4.8 percent after the reaction is carried out for 40min, and the catalyst almost loses activity. The morphology of the aged catalyst was characterized by HRTEM, as shown in fig. 7, it can be seen that the palladium particles on the aged catalyst support were significantly larger than the fresh catalyst, indicating that the prepared catalyst support did not have a good stabilizing effect on the palladium particles. Comparative example 2
Preparing a carrier:
(1) 3.0g of glucose and 2.0g of hexamethylene tetramine are weighed, dissolved in deionized water and stirred for 8 hours at room temperature.
(2) The solution was dried by continuing stirring in an oil bath at 60 ℃.
(3) Transferring the dried sample to a tubular furnace, heating to 300 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 1h at an argon flow rate of 100mL/min, heating to 800 ℃ at a speed of 5 ℃/min under the argon atmosphere, roasting for 2h at an argon flow rate of 100mL/min, and then cooling.
(4) The calcined product was ground into a fine powder in a mortar to obtain a carrier.
The obtained catalyst carrier is composed of a flaky amorphous carbon material modified with nitrogen elements, wherein the nitrogen elements are doped in a carbon material framework in the form of pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and pyridine nitrogen oxide. The BET result showed that the specific surface area of the obtained catalyst carrier was very small, only 63.9m2Per g, total pore volume of 0.07cm3(ii)/g, micropores are almost absent.
Preparing a catalyst:
soaking the catalyst carrier in palladium chloride hydrochloric acid aqueous solution by an isometric soaking method, standing for 12h, drying, then placing in hydrogen for reduction at the hydrogen flow rate of 50mL/min and at 250 ℃ for 2 h.
The morphology of the obtained supported catalyst was characterized by TEM, as shown in fig. 8, wherein the palladium content was 0.5 wt.%, the palladium particles were not uniformly dispersed on the catalyst support, and there were particles with large particle size.
Evaluation of hydrogenation Properties of p-carboxybenzaldehyde:
the hydrogenation reaction of p-carboxybenzaldehyde under the catalysis of a fresh catalyst is carried out in a tank reactor with the volume of 100mL, the reaction is carried out under the conditions of 100 ℃, the hydrogen pressure of 0.5MPa and the stirring speed of 300rpm, the addition amount of the raw materials is 200mg, the addition amount of the catalyst is 20mg, and the addition amount of water is 70 mL. The reaction time was 40min, and the conversion of the starting material was 52.9%. The catalyst aging test is carried out under the conditions of 200 ℃, 1.5MPa of hydrogen pressure and 300rpm of stirring speed, raw materials are not added, the adding amount of the catalyst is 20mg, the adding amount of water is 70mL, and the aging is carried out for 24 hours. After the aging is finished, 200mg of raw material is added, and an activity test is carried out under the same condition with a fresh catalyst, the conversion rate of the raw material is only 11.9 percent after the reaction is carried out for 40min, and the activity of the catalyst is obviously reduced. ICP results show that the content of palladium particles in the aged catalyst is obviously reduced, and the prepared catalyst carrier has no good stabilizing effect on the palladium particles.

Claims (15)

1. The application of a supported catalyst is characterized in that: the catalyst is used for p-carboxybenzaldehyde hydrogenation reaction, glucose oxidation reaction or Suzuki coupling reaction; the catalyst comprises a carrier and an active component, wherein the active component is metal, and the metal loading amount is 0.2-5.0 wt%; the carrier is an amorphous carbon material modified with boron and oxygen; the amorphous carbon material has a sheet-like porous structure; calculated by the weight percentage of the catalyst carrier, the content of carbon element is 85-90%, the content of boron is 1.5-3%, and the content of oxygen element is 8-13%; the specific surface area of the carrier is 800-1800m2Per g, total pore volume of 0.4-1.0cm3(ii)/g, wherein the micropore volume accounts for 60-80% of the total pore volume;
the preparation method of the carrier comprises the following steps:
a) dissolving a carbon source and a boron source in water to obtain a solution 1, and stirring at room temperature for 8-24 h;
b) continuously stirring the solution 1 at the temperature of 50-80 ℃ to dry the solution to obtain a solid 1;
c) transferring the solid 1 to a tubular furnace, roasting for 1-3h at the temperature of 200-400 ℃ in an inert atmosphere, and then heating to the temperature of 600-1200 ℃ for roasting for 1-6h to obtain a product;
d) after naturally cooling to room temperature, grinding the product;
e) and washing and drying the ground product to obtain the carrier of the catalyst.
2. Use according to claim 1, characterized in that: the specific surface area of the carrier is 1000-2Per g, total pore volume of 0.5-0.8cm3/g。
3. Use according to claim 1, characterized in that: the metal is at least one of palladium, platinum, ruthenium, rhodium, cobalt, nickel, iridium and osmium.
4. Use according to claim 1, characterized in that: the boron element and the oxygen element form a bond with the carbon element in a covalent bond mode; the boron element and the carbon element form BC3、BCO2、BC2O、B4At least one of C structure is doped in the carbon material skeleton; the oxygen element and the carbon element form at least one of an ether oxygen structure, a quinone oxygen structure and a hydroxyl oxygen structure, and the oxygen element and the carbon element are doped in the carbon material skeleton.
5. Use according to claim 1 or 2 or 3, characterized in that: the preparation method of the catalyst adopts soluble metal salt solution to carry out impregnation treatment on the carrier, wherein the soluble metal salt solution is at least one of chloride, nitrate and acetate solution of palladium, platinum, ruthenium, rhodium, cobalt, nickel, iridium and osmium.
6. Use according to claim 1, characterized in that: the carbon source is biomass sugar; the boron source is at least one of boric acid, boron trioxide, elemental boron and sodium tetraborate.
7. Use according to claim 6, characterized in that: the carbon source is at least one of glucose, fructose, sucrose, xylose, starch and cellulose.
8. Use according to claim 1, characterized in that: in the step a), the carbon source and the boron source are used in such an amount that the molar ratio of C to B in the solution 1 is 6:5-6: 0.5.
9. Use according to claim 8, characterized in that: in the step a), the dosage of the carbon source and the boron source is such that the molar ratio of C to B in the solution 1 is 3:1-6: 1.
10. Use according to claim 1, characterized in that: in the step c), the inert atmosphere is at least one of argon, nitrogen and helium, and the gas flow rate is 50-150 ml/min; the roasting process is divided into two steps, firstly roasting for 1-3h at the temperature of 200-400 ℃ under the inert atmosphere, and then heating to the temperature of 600-1200 ℃ for roasting for 1-6 h.
11. Use according to claim 10, characterized in that: in the step c), the gas flow rate is 100-; the roasting process is divided into two steps, firstly roasting for 1-1.5h at the temperature of 300 ℃ under the inert atmosphere, and then heating to the temperature of 800 ℃ and roasting for 2-4h at the temperature of 1000 ℃.
12. Use according to claim 1, characterized in that: in the step e), at least one of hot water, ethanol and methanol is used in the washing process.
13. Use according to claim 1, characterized in that: the p-carboxybenzaldehyde hydrogenation reaction specifically comprises the steps of taking p-carboxybenzaldehyde as a raw material, taking water as a reaction solvent, and contacting the raw material with the supported catalyst under the conditions that the reaction temperature is 80-280 ℃ and the hydrogen pressure is 0.1-8MPa to generate p-hydroxymethylbenzoic acid or p-toluic acid.
14. Use according to claim 1, characterized in that: the specific steps of the glucose oxidation reaction are that glucose is used as a raw material, water and alkali solution with a certain concentration are used as a reaction solvent, and the raw material is contacted with the supported catalyst under the conditions that the reaction temperature is 40-80 ℃ and the oxygen pressure is normal pressure to generate gluconate.
15. Use according to claim 1, characterized in that: the Suzuki coupling reaction comprises the specific steps of taking aryl halide and organic boric acid as raw materials, taking water or a mixture of water and an organic solvent as a reaction solvent, adding a certain amount of alkali, and contacting the raw materials with the supported catalyst at the reaction temperature of 30-120 ℃ to generate aromatic hydrocarbon.
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