CN111036198A - Double-shell core-shell structure metal catalyst and preparation method thereof - Google Patents

Double-shell core-shell structure metal catalyst and preparation method thereof Download PDF

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CN111036198A
CN111036198A CN201811189767.8A CN201811189767A CN111036198A CN 111036198 A CN111036198 A CN 111036198A CN 201811189767 A CN201811189767 A CN 201811189767A CN 111036198 A CN111036198 A CN 111036198A
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catalyst
solution
metal
oxide
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CN111036198B (en
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于杨
李忠于
殷玉圣
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Abstract

The invention belongs to the technical field of catalysis, and relates to a core-shell structure metal catalyst and a preparation method thereof. The catalyst comprises an oxide shell layer, a carbon shell layer and a metal core from outside to inside, wherein the oxide shell layer and the carbon shell layer are provided with mesopores. The preparation process comprises the steps of preparing a soluble metal salt solution, adding a surfactant into the metal salt solution and disturbing to obtain a micellar solution of the surfactant; under the conditions of disturbance and pH value control, adding an oxide shell precursor soluble salt solution and a precipitator solution into the micellar solution, filtering, drying, roasting in an inert atmosphere, and forming to obtain the metal @ carbon-oxide double-shell core-shell structure catalyst. The catalyst prepared by the method has high catalytic activity, good selectivity, good carbon deposition resistance and low metal loss rate.

Description

Double-shell core-shell structure metal catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a core-shell structure metal catalyst and a preparation method thereof.
Background
As is well known, the catalyst is widely used in chemical production and plays a role in lifting weight, and the performance of the catalyst is a core element for measuring the overall technical level of the chemical production. The performance indexes of the catalyst mainly comprise activity, selectivity stability, environmental protection and the like, and the first three are main technical indexes. Taking hydrogenation reactions as examples, such as methanol synthesis reaction, butyrolactone preparation by cis-rod hydrogenation, alcohol preparation by aldehyde ketone hydrogenation, selective hydrogenation reaction, etc., these reactions are exothermic reactions, and the catalyst has high requirements for heat sintering resistance and carbon deposition resistance, in addition to high requirements for activity and selectivity of the catalyst. In recent years, the core-shell structure catalyst is widely concerned by catalytic researchers, and the confinement effect of the core-shell structure catalyst can prevent the sintering of metal, so that the purpose of improving the stability of the catalyst is achieved.
Chinese patent CN106179438B discloses a metal @ BN core-shell structure nano-catalyst for methanation reaction of synthesis gas and a preparation method thereof, wherein the catalyst comprises 5-30wt.% of Mx @ (BN) y/SiO2Is adopted in SiO2The surface is dipped with metal salt and then treated in boride solution and nitrogen in sequence to form a surface BN film, thereby achieving the protection effect on metal.
Chinese patentCN105289710B discloses a CO2The catalyst for hydrogenation to prepare isoalkane is prepared through coprecipitation and physical adhesion process to prepare the catalyst with active metal oxide as core and zeolite molecular sieve as shell.
Most of the core-shell structure catalysts prepared by the prior art have shell structures, and the functions of the core-shell structure catalysts are single, and the core-shell structure catalysts mainly prevent active components from sintering and growing.
Disclosure of Invention
The invention aims to provide a core-shell structure catalyst with two shell layers and a preparation method thereof, which have the functions of resisting active component sintering and carbon deposition.
The invention is mainly characterized in that the purposes of protecting the metal and inhibiting the formation of carbon deposition are realized by utilizing a series of creative means such as unique organic structure of micelle, protection of cavity and inlaying effect of metal in carbon after heat treatment, and constructing an oxide protective shell layer by adopting a coprecipitation method.
The invention relates to a double-shell core-shell structure catalyst and a preparation method thereof, which are realized by the following technical scheme: the catalyst comprises an oxide shell layer, a carbon shell layer and a metal core from outside to inside, wherein the oxide shell layer and the carbon shell layer are distributed with mesopores.
Generally, the oxide shell layer is composed of at least one of alumina, zirconia, magnesia and silica, and the most probable pore diameter on the shell layer is 10-50 nm; the most probable pore diameter on the carbon shell is 2-40 nm.
The metal core is composed of at least one of copper, zinc, nickel, palladium, platinum, ruthenium, rhodium, gold and silver.
The preparation method of the catalyst comprises the steps of preparing a soluble metal salt solution, adding a surfactant into the metal salt solution and disturbing to obtain a micellar solution of the surfactant; under the conditions of disturbance and pH value control, adding an oxide shell precursor soluble salt solution and a precipitator solution into the micellar solution, filtering, drying, roasting in an inert atmosphere, and forming to obtain the metal @ carbon-oxide double-shell core-shell structure catalyst.
The surfactant includes one of an anionic surfactant and a nonionic surfactant.
The addition amount of the surfactant is 1.2-5 times of the critical micelle concentration.
The pH value is controlled within the range of 7.2-8.
The mole number of the added soluble salt of the precursor of the shell layer of the oxide is 5-10% of that of the copper in the solution.
The precipitation process is carried out at 30-70 ℃.
The inert atmosphere is one of nitrogen, helium and argon, and the roasting process is to maintain for 2 hours at 300-500 ℃ and then maintain for 1 hour at 600-800 ℃. .
The double-shell core-shell structure catalyst prepared by the method has good activity and selectivity, and has excellent heat sintering resistance and carbon deposition resistance.
Detailed Description
The following examples are provided only for further explanation of the contents and effects of the present invention and are not intended to limit the present invention.
Example 1
Preparing 1L and 1mol/L mixed salt solution of copper nitrate and zinc nitrate, wherein the molar ratio of copper to zinc in the solution is 2/1, adding stearic acid into the mixed salt solution at 30 ℃, and stirring until the concentration of stearic acid is 1.2 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 30 ℃ and controlling the pH value to be 7.2, 0.5mol/L of aluminum nitrate solution and 1mol/L of sodium carbonate solution are added into the micelle solution in a concurrent flow manner, the total adding amount of the aluminum nitrate ensures that the aluminum accounts for 5mol percent of the copper in the solution, the solution is dried for 4 hours at 100 ℃ after being filtered, and is firstly roasted for 2 hours at 300 ℃ and then roasted for 1 hour at 800 ℃ in nitrogen, and finally the plate is made into a cylindrical shape with the diameter of phi 3 multiplied by 3mm, which is defined as Cat-1, the most probable pore diameter of an oxide shell layer is 10nm, and the most probable pore diameter of a carbon shell layer is 2 nm.
The catalyst Cat-1 is used for methanol synthesis reaction, 50mL of catalyst is filled in a fixed bed reactor (i.d. =32 mm), and the feed gas comprises 15% of CO and 50% of CO25%、H265% and the balance N2The space velocity of the raw material gas is 10000h-1The reaction temperature is 300 ℃ and the pressure is 5 MPa. The results show that the reactions were at 100h, 200h andthe space-time yields of methanol at 500h were 1.56, 1.55, 1.58g/gcatAnd h shows that the Cat-1 catalyst has good high-temperature methanol synthesis performance.
Example 2
Preparing 1L of 0.2mol/L palladium nitrate solution, adding alkyl glucoside into the solution at 40 ℃, and stirring until the concentration of the alkyl glucoside is 1.5 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 40 ℃ and controlling the pH value to be 7.8, adding 0.5mol/L zirconium nitrate solution and 1mol/L sodium bicarbonate solution into the micelle solution in a concurrent flow manner, wherein the total adding amount of the zirconium nitrate ensures that the zirconium is 8 mol percent of the palladium in the solution, filtering, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 2 hours in nitrogen, then roasting at 700 ℃ for 1 hour, and finally flaking into a cylinder shape with the diameter of phi 3 multiplied by 3mm, which is defined as Cat-2, wherein the diameter of the most probable pore of an oxide shell layer is 15nm, and the diameter of the most probable pore of a carbon shell layer is 5 nm.
The catalyst Cat-2 is used for the hydrogenation reaction of diisononyl phthalate, 50mL of the catalyst is filled in a fixed bed reactor (i.d. =32 mm), and the hourly space velocity of diisononyl phthalate liquid is 0.8h-1The hydrogen-ester ratio is 50, the reaction temperature is 200 ℃, and the pressure is 8 MPa. The result shows that the conversion rate of diisononyl phthalate and the selectivity of diisononyl cyclohexane-1, 2-dicarboxylate are 98.5% and 96.8% respectively at 500h, no Pd loss exists, and the Cat-2 catalyst has good activity, selectivity and precious metal loss resistance.
Example 3
Preparing 1L of 0.2mol/L ruthenium nitrate solution, adding fatty glyceride into the solution at 50 ℃, and stirring until the concentration of the fatty glyceride is 2 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 50 ℃ and controlling the pH value to be 8.0, adding 0.5mol/L zirconium nitrate solution and 1mol/L sodium bicarbonate solution into the micelle solution in a concurrent flow manner, wherein the total adding amount of the zirconium nitrate ensures that the mol number of the zirconium is 10 percent of that of ruthenium in the solution, drying for 4 hours at 100 ℃ after filtering, roasting for 2 hours at 500 ℃ in nitrogen, then roasting for 1 hour at 600 ℃, and finally flaking into a cylinder shape with the diameter of phi 3 multiplied by 3mm, which is defined as Cat-3, wherein the diameter of the most probable pore of an oxide shell layer is 20nm, and the diameter of the most probable pore of a carbon shell layer is 10 nm.
The catalyst Cat-3 is used for the hydrogenation reaction of diisononyl phthalate, 50mL of the catalyst is filled in a fixed bed reactor (i.d. =32 mm), and the hourly space velocity of diisononyl phthalate liquid is 0.6h-1The hydrogen-ester ratio is 20, the reaction temperature is 220 ℃, and the pressure is 6 MPa. The result shows that the conversion rate of diisononyl phthalate and the selectivity of diisononyl cyclohexane-1, 2-dicarboxylate are 99.2% and 97.8% respectively at 500h, and Ru loss does not occur, which indicates that the Cat-3 catalyst has good activity, selectivity and precious metal loss resistance.
Example 4
Preparing 1L of 0.5mol/L silver nitrate solution, adding the sorbitan fatty acid into the solution at 60 ℃, and stirring until the concentration of the sorbitan fatty acid is 3 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 60 ℃ and controlling the pH value to be 7.2, 0.5mol/L of silica sol solution and 1mol/L of sodium carbonate solution are added into the micelle solution in a concurrent flow manner, the total adding amount of the silica sol ensures that the mole number of the silver in the solution is 4%, the solution is dried for 4 hours at 100 ℃ after being filtered, and is firstly roasted for 2 hours at 300 ℃ in nitrogen and then roasted for 1 hour at 800 ℃, and finally the solution is sliced into a cylinder shape with the diameter of phi 3 multiplied by 3mm, which is defined as Cat-4, the diameter of most probable pore of an oxide shell is 25nm, and the diameter of most probable pore of a carbon shell is 15 nm.
The Cat-4 catalyst is used for the reaction of synthesizing 2-methylindole from aniline and 1, 2-propylene glycol, 50mL of the catalyst is filled in a fixed bed reactor (phi 32 mm), the reaction temperature is 250 ℃, the reaction pressure is normal pressure, the gas phase reaction retention time is 0.5 second, the volume fraction of hydrogen added in gas phase feed is 5%, the volume fraction of water vapor added is 0.5%, the reacted gas phase material enters a condenser for condensation, condensate liquid is collected for oil-water separation, the oil phase composition is detected, and the 1, 2-propylene glycol conversion rate and the 3-methylindole yield are calculated. The result shows that the conversion rate of 1, 2-propylene glycol is 99.8% and the yield of 3-methylindole is 61.5% when the reaction is carried out for 500h, Ag on the catalyst is not lost, and no carbon deposition or coking is generated on the surface of the catalyst, which indicates that the Cat-4 catalyst has good activity, selectivity, precious metal loss resistance and carbon deposition resistance.
Example 5
Preparing 1L of 0.5mol/L silver nitrate solution, adding polysorbate into the solution at 70 ℃, and stirring until the polysorbate concentration is 4 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 70 ℃ and controlling the pH value to be 7.5, 0.5mol/L of aluminum nitrate solution and 1mol/L of ammonia water are added into the micelle solution in a concurrent flow manner, the total adding amount of the aluminum nitrate ensures that the aluminum accounts for 3mol percent of the silver in the solution, the solution is dried for 4 hours at 100 ℃ after being filtered, and is roasted for 2 hours at 300 ℃ in argon, then is roasted for 1 hour at 800 ℃, and finally is flaked into a cylindrical shape with phi of 3 multiplied by 3mm, which is defined as Cat-5, the diameter of the most probable pore of an oxide shell layer is 30nm, and the diameter of the most probable pore of a carbon shell layer is 25 nm.
The Cat-5 catalyst is used for the reaction of synthesizing 2-methylindole from aniline and 1, 2-propylene glycol, 50mL of the catalyst is filled in a fixed bed reactor (phi 32 mm), the reaction temperature is 250 ℃, the reaction pressure is normal pressure, the gas phase reaction retention time is 0.5 second, the volume fraction of hydrogen added in gas phase feed is 5%, the volume fraction of water vapor added is 0.5%, the reacted gas phase material enters a condenser for condensation, condensate liquid is collected for oil-water separation, the oil phase composition is detected, and the 1, 2-propylene glycol conversion rate and the 3-methylindole yield are calculated. The result shows that the conversion rate of 1, 2-propylene glycol is 99.2% and the yield of 3-methylindole is 60.7% when the reaction is carried out for 500 hours, Ag on the catalyst is not lost, and no carbon deposition or coking is generated on the surface of the catalyst, which shows that the Cat-4 catalyst has good activity, selectivity, precious metal loss resistance and carbon deposition resistance.
Example 6
Preparing 1L of 0.3mol/L silver nitrate solution, adding polysorbate into the solution at 60 ℃, and stirring until the polysorbate concentration is 2.5 times of the critical micelle concentration to obtain a micelle solution; under the conditions of stirring at 70 ℃ and controlling the pH value to be 7.3, 0.5mol/L of aluminum nitrate solution and 1mol/L of ammonia water are added into the micelle solution in a concurrent flow manner, the total adding amount of the aluminum nitrate ensures that the aluminum accounts for 2mol percent of the silver in the solution, the solution is dried for 4 hours at 100 ℃ after being filtered, and is firstly roasted for 2 hours at 300 ℃ in argon and then roasted for 1 hour at 800 ℃, and finally the plate is made into a cylindrical shape with phi of 3 multiplied by 3mm and defined as Cat-6, the diameter of the most probable pore of an oxide shell layer is 50nm, and the diameter of the most probable pore of a carbon shell layer is 40 nm.
The Cat-6 catalyst is used for the reaction of synthesizing 2-methylindole from aniline and 1, 2-propylene glycol, 50mL of the catalyst is filled in a fixed bed reactor (phi 32 mm), the reaction temperature is 250 ℃, the reaction pressure is normal pressure, the gas phase reaction retention time is 0.5 second, the volume fraction of hydrogen added in gas phase feed is 5%, the volume fraction of water vapor added is 0.5%, the reacted gas phase material enters a condenser for condensation, condensate liquid is collected for oil-water separation, the oil phase composition is detected, and the 1, 2-propylene glycol conversion rate and the 3-methylindole yield are calculated. The result shows that the conversion rate of 1, 2-propylene glycol is 99.9% and the yield of 3-methylindole is 62.8% when the reaction is carried out for 500h, Ag on the catalyst is not lost, and no carbon deposition or coking is generated on the surface of the catalyst, which indicates that the Cat-4 catalyst has good activity, selectivity, precious metal loss resistance and carbon deposition resistance.
Example 7
Preparing 1L and 1mol/L nickel nitrate solution, adding polysorbate into the solution at 70 ℃ and stirring until the polysorbate concentration is 5 times of the critical micelle concentration to obtain micelle solution; under the conditions of stirring at 70 ℃ and controlling the pH value to be 7.2, 0.5mol/L of aluminum nitrate solution and 1mol/L of ammonia water are added into the micelle solution in a concurrent flow manner, the total addition of the aluminum nitrate ensures that the aluminum accounts for 4 mol percent of the nickel in the solution, the solution is dried for 4 hours at 100 ℃ after being filtered, and is firstly roasted for 2 hours at 300 ℃ in argon and then roasted for 1 hour at 800 ℃, and finally the plate is made into a cylindrical shape with phi of 3 multiplied by 3mm, which is defined as Cat-7, the diameter of the most probable pore of an oxide shell is 12nm, and the diameter of the most probable pore of a carbon shell is 10 nm.
The Cat-7 catalyst is used for the reaction of preparing methane from synthesis gas, 50mL of the catalyst is filled in a fixed bed reactor (phi 32 mm), and the feed gas comprises 8.02% of CO and 50% of CO23.22%、H236.35%、N252.51 percent and the space velocity is 20000h-1The inlet temperature is 290 ℃, and the pressure is 3 MPa. The results show that at 500h the reaction time is 100% CO conversion2Conversion rate is 65%, and outlet gas CH4The volume content is 55 percent, and the surface of the catalyst does not have any carbon deposit or coking.

Claims (10)

1. A double-shell core-shell structure metal catalyst is characterized in that the catalyst comprises an oxide shell layer, a carbon shell layer and a metal core from outside to inside, and mesoporous distribution is formed on the oxide shell layer and the carbon shell layer.
2. The catalyst according to claim 1, wherein the oxide shell is composed of at least one of alumina, zirconia, magnesia, and silica, and the most probable pore diameter on the shell is 10 to 50 nm; the most probable pore diameter on the carbon shell is 2-40 nm.
3. The catalyst of claim 1 wherein the metal core is comprised of at least one of copper, zinc, nickel, palladium, platinum, ruthenium, rhodium, gold, and silver.
4. The method for preparing the catalyst according to claim 1, wherein a soluble metal salt solution is prepared, and the surfactant is added to the metal salt solution and disturbed to obtain a micellar solution of the surfactant; under the conditions of disturbance and pH value control, adding an oxide shell precursor soluble salt solution and a precipitator solution into the micellar solution, filtering, drying, roasting in an inert atmosphere, and forming to obtain the metal @ carbon-oxide double-shell core-shell structure catalyst.
5. The method of claim 4, wherein the surfactant comprises one of an anionic surfactant and a nonionic surfactant.
6. The method according to claim 4, wherein the surfactant is added in an amount of 1.2 to 5 times the critical micelle concentration.
7. The method according to claim 4, wherein the pH is controlled to be in the range of 7.2 to 8.
8. The method of claim 4, wherein the soluble salt of the oxide shell precursor is added in a molar amount of 5% to 10% of the molar amount of copper in the solution.
9. The method according to claim 4, wherein the precipitation is carried out at a temperature of 30 to 70 ℃.
10. The method according to claim 4, wherein the inert gas is one of nitrogen, helium and argon, and the calcination is performed at 300-500 ℃ for 2 hours and then at 600-800 ℃ for 1 hour.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111558374A (en) * 2020-05-28 2020-08-21 中国科学院兰州化学物理研究所 Supported catalyst, preparation method thereof and method for catalytically synthesizing N-ethylaniline
CN112724064A (en) * 2020-12-30 2021-04-30 广州星业新材料有限公司 Method for preparing 5, 6-dihydroxyindole by using modified ordered mesoporous carbon supported metal catalyst
WO2021218176A1 (en) * 2020-04-28 2021-11-04 浙江卫星能源有限公司 Yolk-shell sio2-al2o3 noble metal propane dehydrogenation catalyst and preparation method therefor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861592A (en) * 2014-04-02 2014-06-18 北京化工大学 Method for preparing Au@ CeO2 hollow core-shell nanometer material
CN105056849A (en) * 2015-07-15 2015-11-18 浙江大学 Hollow sphere adopting metal oxide/Pt/C three-layer nano structure and preparation method of hollow sphere
CN105251491A (en) * 2015-11-09 2016-01-20 中国科学院化学研究所 Catalyst for preparing 2,5-dimethylfuran through selective hydrogenolysis of 5-hydroxymethylfurfural and preparation method of catalyst
CN105289710A (en) * 2015-11-16 2016-02-03 中国科学院山西煤炭化学研究所 Catalyst for preparation of isoalkanes by hydrogenation of carbon dioxide as well as preparation method and application thereof
CN107552054A (en) * 2017-08-18 2018-01-09 南昌大学 A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method
CN108380197A (en) * 2017-11-23 2018-08-10 天津工业大学 A kind of methane CO based on microwave activation2Preparing synthetic gas by reforming nucleocapsid catalyst and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861592A (en) * 2014-04-02 2014-06-18 北京化工大学 Method for preparing Au@ CeO2 hollow core-shell nanometer material
CN105056849A (en) * 2015-07-15 2015-11-18 浙江大学 Hollow sphere adopting metal oxide/Pt/C three-layer nano structure and preparation method of hollow sphere
CN105251491A (en) * 2015-11-09 2016-01-20 中国科学院化学研究所 Catalyst for preparing 2,5-dimethylfuran through selective hydrogenolysis of 5-hydroxymethylfurfural and preparation method of catalyst
CN105289710A (en) * 2015-11-16 2016-02-03 中国科学院山西煤炭化学研究所 Catalyst for preparation of isoalkanes by hydrogenation of carbon dioxide as well as preparation method and application thereof
CN107552054A (en) * 2017-08-18 2018-01-09 南昌大学 A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method
CN108380197A (en) * 2017-11-23 2018-08-10 天津工业大学 A kind of methane CO based on microwave activation2Preparing synthetic gas by reforming nucleocapsid catalyst and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021218176A1 (en) * 2020-04-28 2021-11-04 浙江卫星能源有限公司 Yolk-shell sio2-al2o3 noble metal propane dehydrogenation catalyst and preparation method therefor
CN111558374A (en) * 2020-05-28 2020-08-21 中国科学院兰州化学物理研究所 Supported catalyst, preparation method thereof and method for catalytically synthesizing N-ethylaniline
CN112724064A (en) * 2020-12-30 2021-04-30 广州星业新材料有限公司 Method for preparing 5, 6-dihydroxyindole by using modified ordered mesoporous carbon supported metal catalyst

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