CN116060012A - SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof - Google Patents

SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof Download PDF

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CN116060012A
CN116060012A CN202111276375.7A CN202111276375A CN116060012A CN 116060012 A CN116060012 A CN 116060012A CN 202111276375 A CN202111276375 A CN 202111276375A CN 116060012 A CN116060012 A CN 116060012A
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sio
catalyst
supported
nickel
reaction
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贾丹丹
赵杰
朱忠朋
闫瑞
伏朝林
郑伟平
李雅楠
陶志平
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present disclosure relates to a SiO 2 Supported Ni catalyst, preparation method and application thereof, and SiO 2 The supported Ni catalyst comprises a carrier and Ni particles supported on the carrier; wherein the carrier is SiO 2 The Ni particles have an average particle diameter of 10nm or less. SiO prepared by the method 2 The active component Ni in the supported Ni catalyst is uniformly distributed, and the average particle diameter of Ni particles in the catalyst is less than 10nm, so that the catalyst has excellent catalytic effect, and can obtain higher raw material conversion rate and bridge type tetrahydrodicyclopentadiene selectivity when being used for the catalytic hydrogenation reaction of dicyclopentadiene.

Description

SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof
Technical Field
The present disclosure relates to the field of petrochemical technology, and in particular, to a SiO 2 Supported Ni catalyst, its preparation method and application.
Background
With the increasing scale of ethylene and petroleum catalytic cracker, the C5 fraction resources are increasingly abundant. Dicyclopentadiene (DCPD) has become a hotspot in the petrochemical field as the most important fraction for C5 separation, how to digest applications. Tetrahydrodicyclopentadiene (endo-THDCPD) can be prepared by hydrogenating DCPD. Endo-THDCPD is a solid fuel with high energy density, and is simultaneously an intermediate for synthesizing fuel-hanging tetrahydrodicyclopentadiene or an intermediate for synthesizing adamantane which is a fine chemical raw material with extremely high added value.
At present, raney nickel catalyst which is put into industrial use has higher hydrogenation activity of DCPD, but the catalyst is easy to be naturally stored in the air, is not easy to be stored, has shorter service life and is not easy to be regenerated and used. In addition, many of the DCPD hydrogenation activities are noble metals, but the applications are limited due to their high price and low sources. The non-noble metal nickel-based catalyst reported at present has the problems of low activity and poor stability, so the invention aims to develop a novel non-noble metal catalyst to realize high-efficiency catalytic hydrogenation of dicyclopentadiene.
Disclosure of Invention
The purpose of the present disclosure is to provide a SiO 2 Supported Ni catalyst, preparation method and application thereof, siO 2 Ni particles in supported Ni catalystsThe catalyst has smaller average particle diameter and excellent hydrogenation performance, and can obtain higher raw material selectivity and bridge type tetrahydrodicyclopentadiene selectivity when being applied to hydrogenation reaction of dicyclopentadiene.
To achieve the above object, a first aspect of the present disclosure provides SiO 2 Supported Ni catalyst, said SiO 2 The supported Ni catalyst comprises a carrier and Ni particles supported on the carrier;
wherein the carrier is SiO 2 The Ni particles have an average particle diameter of 10nm or less.
Optionally in the form of said SiO 2 The mass fraction of Ni element is 2-9% based on the total weight of the supported Ni catalyst.
A second aspect of the present disclosure provides for the preparation of SiO 2 A method of loading a Ni catalyst, the method comprising the steps of:
s1 SiO is prepared from 2 Mixing with nickel source, and performing impregnation treatment to obtain impregnated SiO 2 ；
S2, soaking the impregnated SiO 2 Mixing 2-methylimidazole with a first solvent, and carrying out contact reaction to obtain a precursor material;
s3, carrying out heat treatment on the precursor material in a reducing atmosphere;
wherein the SiO is 2 The particle size of (2) is 200-400nm.
Optionally in step S1, the SiO 2 The molar ratio of the nickel source to the nickel element is (20-90): 1.
optionally the nickel source is used in the form of a solution containing a second solvent comprising one or more of water, ethanol, methanol and acetone;
the nickel source comprises one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
in step S2, the first solvent includes one or more of water, ethanol, methanol, acetone, N-dimethylformamide and ammonia water;
optionally, the molar ratio of the nickel source to the 2-methylimidazole, calculated as nickel element, is (0.1-5): 1.
optionally the conditions of the impregnation treatment include: stirring for 8-48h at 20-80deg.C;
in step S2, the conditions of the contact reaction include: stirring for 0.1-48 hr at 50-150deg.C;
in step S3, the heat treatment conditions include: the temperature is 300-900 ℃ and the time is 2-8h.
Optionally step S1 further comprises: the SiO is subjected to 2 Mixing and stirring the solution containing nickel source, carrying out the dipping treatment, carrying out solid-liquid separation on the first reaction material obtained by the reaction, and drying the obtained first solid material to obtain the dipped SiO 2 ；
Step S2 further includes: the impregnated SiO is subjected to 2 Dispersing in the first solvent, adding the 2-methylimidazole into the obtained mixed material, carrying out the contact reaction, carrying out solid-liquid separation on the second reaction material obtained by the reaction, and drying the obtained second solid material to obtain the precursor material;
optionally, the impregnated SiO is based on the volume of the first solvent 2 The dosage of (2) is 0.5-1.5mol/mL;
optionally, in step S3, the reducing atmosphere includes a hydrogen-argon mixture and/or a hydrogen-nitrogen mixture.
A third aspect of the present disclosure provides SiO prepared by the method of the second aspect of the present disclosure 2 Supported Ni catalyst.
A fourth aspect of the present disclosure provides a method of producing a SiO according to the first or third aspect of the present disclosure 2 The supported Ni catalyst is applied to dicyclopentadiene catalytic hydrogenation reaction.
Optionally, the conditions of the catalytic reaction include: the reaction temperature is 40-200 ℃, the hydrogen pressure is 0.5-6MPa, the reaction time is 0.2-20h, and the stirring speed is high: 400-1000r/min of the SiO 2 The mass ratio of the supported Ni catalyst to the dicyclopentadiene is 1: (5-20);
optionally, the catalytic hydrogenation reaction is performed in a third solvent, wherein the third solvent is selected from one or more of methylcyclohexane, cyclohexane and n-hexane.
By the technical proposal, the application adopts SiO 2 The precursor material which is used as a carrier and loaded with the Ni MOFs material is subjected to heat treatment to obtain SiO 2 The supported Ni catalyst can avoid the aggregation of active component nickel in the prepared catalyst, realize the uniform distribution of active components, ensure that the average particle size of Ni particles in the catalyst is less than 10nm, ensure that the catalyst has excellent catalytic effect, reduce the dosage of Ni, and obtain higher raw material conversion rate and bridge type tetrahydrodicyclopentadiene selectivity when being used for the catalytic hydrogenation reaction of dicyclopentadiene.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a SiO produced in example 1 2 XRD diffractogram of supported Ni catalyst A1.
FIG. 2 is a SiO produced in example 1 2 SEM image of supported Ni catalyst A1.
FIG. 3 is a SiO produced in example 1 2 HRTEM plot of supported Ni catalyst A1.
FIG. 4 is an infrared spectrum of the precursor material prepared in example 1 and Ni ZIF.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a SiO 2 Supported Ni catalyst, said SiO 2 The supported Ni catalyst comprises a supportAnd Ni particles supported on the carrier;
wherein the carrier is SiO 2 The Ni particles have an average particle diameter of 10nm or less.
In a preferred embodiment of the present disclosure, the Ni particles have an average particle size of 5-10nm. Wherein the Ni particles comprise elemental Ni, preferably all Ni elements are present in elemental form.
In one embodiment of the present disclosure, siO 2 The mass fraction of Ni element is 2-9%, preferably 2-5% in terms of mass fraction based on the total weight of the supported Ni catalyst. SiO satisfying the above conditions 2 When the supported Ni catalyst is applied to the catalytic hydrogenation reaction of dicyclopentadiene, the conversion rate of raw materials and the selectivity of bridge-type tetrahydrodicyclopentadiene can be effectively improved on the premise of lower nickel loading, and a better catalytic effect is obtained.
A second aspect of the present disclosure provides for the preparation of SiO 2 A method of loading a Ni catalyst, the method comprising the steps of:
s1 SiO is prepared from 2 Mixing with nickel source, and performing impregnation treatment to obtain impregnated SiO 2 ；
S2, soaking the impregnated SiO 2 Mixing 2-methylimidazole with a first solvent, and carrying out contact reaction to obtain a precursor material;
s3, carrying out heat treatment on the precursor material in a reducing atmosphere;
wherein the SiO is 2 The particle size of (2) is 200-400nm.
SiO satisfying the above average particle diameter range 2 The problem of poor loading effect caused by too large or too small particle size is avoided. And SiO with the average particle diameter is adopted 2 The Ni particles in the prepared catalyst have smaller particle size, which is beneficial to improving the catalytic performance.
In one embodiment of the present disclosure, in step S3, the reducing atmosphere includes a hydrogen-argon mixture and/or a hydrogen-nitrogen mixture. Wherein, the volume ratio of hydrogen to nitrogen in the hydrogen-nitrogen mixed gas is 1: (0.5-2), wherein the volume ratio of hydrogen to argon in the hydrogen-argon mixture is 1: (0.5-2). Specifically, the reducing atmosphere may be a hydrogen-nitrogen mixture gas with a volume ratio of 1:1.
In the present disclosure, step S2 is to deposit SiO 2 Compounding the carrier with the Ni MOFs material, and performing heat treatment in the step S3 to obtain SiO 2 The method can reduce the aggregation degree of the active component Ni, so that the average particle size of Ni particles in the Ni catalyst is less than 10nm, and further higher dispersity of active metal is obtained.
In one embodiment of the present disclosure, in step S1, siO 2 The molar ratio of the catalyst to the nickel source calculated as nickel element is (20-90): 1, preferably (20-60): 1.
in the present disclosure, siO used in step S1 2 The preparation can be carried out by the following method:
mixing a silicon source with a fourth solvent, reacting, performing solid-liquid separation and drying to obtain SiO 2 . The silicon source comprises ethyl orthosilicate and/or a silica sol, which may be, for example, ethyl orthosilicate. The fourth solvent comprises one or more of water, ethanol, methanol and acetone, preferably a mixture of water and ethanol. Wherein the volume ratio of water to ethanol is (0.1-8): 1, preferably (0.1-4): 1, a step of; the volume ratio of water to ammonia water is (0.1-8): 1 ", preferably (0.1-4): 1. the volume ratio of the silicon source to the fourth solvent calculated as silicon element is (0.01-0.30): 1, preferably (0.01-0.2): 1. the reaction time is 5-24h, and the temperature is 20-70 ℃; preferably, the time is 5-12 hours and the temperature is 20-50 ℃. SiO prepared by the method 2 The particle size of (2) is 200-400nm.
In one embodiment of the present disclosure, the molar ratio of the silicon source in elemental silicon to the nickel source in elemental nickel is (1-30): 1, preferably (1-20): 1.
in one embodiment of the present disclosure, in step S1, the nickel source is used in the form of a solution containing a second solvent including one or more of water, ethanol, methanol, and acetone; for example, water.
In one embodiment of the present disclosure, the nickel source comprises one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate; preferably one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate, for example, nickel nitrate.
In one embodiment of the present disclosure, in step S2, the first solvent includes one or more of water, ethanol, methanol, acetone, N-dimethylformamide, and aqueous ammonia; preferably comprises one or more of water, ethanol, methanol, acetone and N, N-dimethylformamide; for example, methanol is possible.
In one embodiment of the present disclosure, the molar ratio of nickel source to 2-methylimidazole, calculated as elemental nickel, is (0.1-5): 1, preferably (0.1-3): 1.
in one embodiment of the present disclosure, in step S1, the conditions of the impregnation treatment include: the dipping treatment is carried out under the condition of stirring for 8-48h at 20-80 ℃; preferably, the time is 8-24 hours and the temperature is 20-60 ℃.
In one embodiment of the present disclosure, in step S2, the conditions of the contact reaction include: stirring for 0.1-72 hr at 50-150deg.C; preferably, the time is 0.1-24 hours and the temperature is 50-100 ℃. In another embodiment, stirring is performed for 10-30 minutes without heating, and then heating is turned on to continue stirring.
In the present disclosure, the stirring means is conventional in the art, and may be magnetic stirring, for example.
In step S3, the conditions of the heat treatment include: the temperature is 300-900 ℃ and the time is 2-8h; preferably, the temperature is 400-800 ℃ and the time is 2-5h. Meeting the heat treatment conditions can ensure that the Ni MOF material is fully pyrolyzed to obtain active metal Ni particles.
In one embodiment of the present disclosure, step S1 further includes: siO is made of 2 Mixing with solution containing nickel source, stirring, soaking, separating solid from liquid, drying to obtain impregnated SiO 2 。
In one embodiment of the present disclosure, step S2 further includes: the impregnated SiO is subjected to 2 Dispersing in a first solvent, and mixingAdding 2-methylimidazole into the materials, performing contact reaction, performing solid-liquid separation on the second reaction material obtained by the reaction, and drying the obtained second solid material to obtain the precursor material.
In one embodiment of the present disclosure, the impregnated SiO is based on the volume of the first solvent 2 The amount of (C) is 0.5-1.5mol/mL, preferably 1-1.5mol/mL.
In the present disclosure, the manner of drying is conventional in the art, and may be, for example, heat drying.
A third aspect of the present disclosure provides SiO prepared by the method of the second aspect of the present disclosure 2 Supported Ni catalyst.
SiO provided by the third aspect of the disclosure 2 Supported Ni catalyst with SiO provided in the first aspect of the disclosure 2 The supported Ni catalyst has the same structure and properties.
A fourth aspect of the present disclosure provides a method of producing a SiO according to the first or third aspect of the present disclosure 2 The supported Ni catalyst is applied to dicyclopentadiene catalytic hydrogenation reaction.
In one embodiment of the present disclosure, the conditions of the catalytic reaction include: the reaction temperature is 40-200 ℃, the hydrogen pressure is 0.5-6MPa, the reaction time is 0.2-20h, and the SiO is the catalyst 2 The mass ratio of the supported Ni catalyst to dicyclopentadiene is 1: (5-20); preferably, the reaction temperature is 40-140 ℃, the hydrogen pressure is 0.5-5MPa, the reaction time is 0.5-12h, and the SiO is 2 The mass ratio of the supported Ni catalyst to dicyclopentadiene is 1: (5-15). Dicyclopentadiene is conventional in the art, and is not particularly limited, and may be, for example, dicyclopentadiene having a purity of 85 to 99%.
In the present disclosure, the stirring speed of the catalytic hydrogenation reaction may be 400 to 1000r/min, preferably 400 to 800r/min.
In one embodiment of the present disclosure, the catalytic hydrogenation reaction is performed in a third solvent selected from one or more of methylcyclohexane, cyclohexane and n-hexane, and may be methylcyclohexane, for example.
The present invention will be described in further detail by examplesSiO of the disclosure 2 The supported Ni catalyst and the application thereof in dicyclopentadiene catalytic hydrogenation reaction. The starting materials used in the examples are all available commercially.
XRD diffraction instrument model is Panalytical.
The ICP test instrument model is: agilent ICPOES730.
The infrared spectrum test instrument has the following model: nicolet 6700.
The instrument model of the HRTEM test is as follows: JEM-2100.
The instrument model of SEM test is: FESEM, SU-70.
The average particle diameter of the metal Ni particles was measured by: the particle size of the metal is observed and counted under a TEM electron microscope, and the model of a TEM instrument is JEM-2100.
The dicyclopentadiene conversion and the selectivity of the bridge tetrahydrodicyclopentadiene in the application are calculated by gas chromatography by using a peak area normalization method. Wherein the gas chromatograph instrument model is Agilent gas chromatograph 7890B.
Conversion = (1-dicyclopentadiene peak area percentage) ×100%
Figure BDA0003330046870000081
In the above calculation formula, the dicyclopentadiene peak area percentage refers to the percentage of the peak area of the remaining dicyclopentadiene to the peak area of all substances after the reaction is completed, and all substances include all products and the remaining dicyclopentadiene.
Example 1
The following procedure was employed to prepare the SiO of the present application 2 Supported Ni catalyst.
(1) Preparing a mixed solution of ethanol and water, adding tetraethoxysilane and ammonia water into the mixed solution, stirring the mixture for 6 hours at 25 ℃, and centrifugally drying the mixture to obtain SiO 2 The particle size was 300nm. The testing method comprises the following steps: and (3) observing and counting under a TEM (Transmission electron microscope) instrument model JEM-2100.
(2) SiO obtained in the step (1) is reacted with 2 Mixing with nickel nitrate solutionStirring at 45deg.C for 6 hr, and drying to obtain impregnated SiO 2 。
(3) Soaking the impregnated SiO obtained in the step (2) 2 Mixing with methanol and 2-methylimidazole, stirring at 70deg.C for 1 hr, and centrifuging and drying to obtain precursor material.
(4) Heat-treating the precursor material at 500 ℃ for 4 hours under the hydrogen-nitrogen mixed gas to obtain SiO 2 The supported Ni/C particle catalyst was designated catalyst A1.
FIG. 1 is a SiO produced in example 1 2 XRD diffractogram of supported Ni catalyst A1.
FIG. 2 is a SiO produced in example 1 2 SEM image of the supported Ni catalyst A1, it can be seen that SiO 2 Ni particles uniformly grow on the particles.
FIG. 3 is a SiO produced in example 1 2 The HRTEM image of the supported Ni catalyst A1, as can be seen, the interplanar spacing of the small particles is 2.01 angstroms, corresponding to the (111) crystal plane of metallic Ni, demonstrating SiO 2 The long particles on the support are Ni particles.
The precursor material prepared in example 1 and the Ni ZIF were subjected to infrared spectrum test, and the result is shown in FIG. 4, wherein ZIF characteristic peaks appear in the precursor, wherein 1430cm -1 The peaks of (2) are attributed to the backbone vibration of 2-methylimidazole, proving that the precursor material has a ZIF structure.
Taking the catalyst A1 to perform dicyclopentadiene (DCPD) catalytic hydrogenation reaction in a high-pressure reaction kettle, wherein the solvent is methylcyclohexane, and the mass fraction of dicyclopentadiene is 10%; the mass ratio of the catalyst A1 to dicyclopentadiene is 1:10; the reaction temperature is 90 ℃, the hydrogen pressure is 3MPa, the reaction time is 1h, and the stirring speed is 600r/min. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1. The mass fraction of Ni element is tested by ICP.
Wherein the volume ratio of water to ethanol is 0.27:1; the volume ratio of water to ammonia water is 3.75:1; the ratio of the total volume of silicon source to ethanol and water was 0.043:1, a step of; siO (SiO) 2 The molar ratio of the nickel source to the nickel element is 60:1, a step of; nickel in terms of nickel elementThe molar ratio of the source to the 2-methylimidazole was 0.23:1, based on the volume of methanol, siO after impregnation 2 The dosage of (2) is 1.3mol/mL; the volume ratio of hydrogen to nitrogen in the hydrogen-nitrogen mixed gas is 1:1.
Example 2
Catalyst A2 was prepared by the method of example 1, except that the heat treatment in step (4) was carried out at 550℃for 6 hours.
Taking the catalyst A2 to perform dicyclopentadiene (DCPD) catalytic hydrogenation reaction in a high-pressure reaction kettle, wherein the solvent is methylcyclohexane, and the mass fraction of dicyclopentadiene is 10%; the mass ratio of the catalyst A2 to dicyclopentadiene is 1:8; the reaction temperature is 90 ℃, the hydrogen pressure is 3MPa, the reaction time is 3h, and the stirring speed is 600r/min. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
Wherein the volume ratio of water to ethanol is 0.27:1; the volume ratio of water to ammonia water is 3.75:1; the ratio of the total volume of silicon source to ethanol and water was 0.043:1, a step of; siO (SiO) 2 The molar ratio of the nickel source to the nickel element is 60:1, a step of; the molar ratio of the nickel source to the 2-methylimidazole calculated as nickel element was 0.23:1.
Example 3
Catalyst A3 was prepared by the method of example 1, except for SiO 2 The molar ratio of the nickel source to the nickel element is 40:1, a step of; the molar ratio of the nickel source to the 2-methylimidazole calculated as nickel element is 0.2:1.
Taking the catalyst A3 to perform dicyclopentadiene (DCPD) catalytic hydrogenation reaction in a high-pressure reaction kettle, wherein the solvent is methylcyclohexane, and the mass fraction of dicyclopentadiene is 10%; the mass ratio of the catalyst A3 to dicyclopentadiene is 1:8; the reaction temperature is 90 ℃, the hydrogen pressure is 3MPa, the reaction time is 3h, and the stirring speed is 600r/min. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
Example 4
Catalyst A4 was prepared by the method of example 1, except that nickel acetate was used as the nickel source. Catalyst A4 was used for the catalytic hydrogenation of dicyclopentadiene under the same reaction conditions as in example 1. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
Comparative example 1
Synthesis of SiO according to example 1 2 Then, ni is loaded on SiO by a conventional wet impregnation method 2 The SiO is obtained by adopting a conventional two-step method of air calcination (heating for 3h at 450 ℃) and hydrogen reduction (heating for 2h at 450 ℃) 2 The supported Ni catalyst was designated as D1. Catalyst D1 was used for the catalytic hydrogenation of dicyclopentadiene under the same reaction conditions as in example 1. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
Comparative example 2
Catalyst D2 was prepared by the method of example 1, except that the SiO obtained in step (1) was reacted 2 Mixing nickel nitrate solution, methanol and 2-methylimidazole, stirring at 70 ℃ for 1h, centrifugally drying, and carrying out heat treatment on the dried solid at 500 ℃ for 4h under a hydrogen-nitrogen mixed gas to obtain the catalyst D2.
Catalyst D2 was used for the catalytic hydrogenation of dicyclopentadiene under the same reaction conditions as in example 1. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
Comparative example 3
Catalyst D3 was prepared by the method of example 1, except that a commercial SiO was used 2 (20 nm) as a carrier. Catalyst D3 was used for the catalytic hydrogenation of dicyclopentadiene under the same reaction conditions as in example 1. The conversion of raw materials, the selectivity of products, the mass fraction of Ni element and the average particle diameter of the metallic Ni particles are shown in Table 1.
TABLE 1
Figure BDA0003330046870000111
Figure BDA0003330046870000121
From the data in Table 1, it can be seen that the present application will use SiO 2 Preparation of SiO by heat treatment of precursor Material that is Carrier and Supported with Ni MOFs Material 2 The average grain diameter of Ni particles in the supported Ni catalyst prepared by the method is below 10nm, and the catalyst has excellent catalytic performance, and can obtain higher raw material conversion rate and bridge type tetrahydrodicyclopentadiene selectivity when being applied to the catalytic hydrogenation reaction of dicyclopentadiene.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. SiO (silicon dioxide) 2 The supported Ni catalyst is characterized in that the SiO 2 The supported Ni catalyst comprises a carrier and Ni particles supported on the carrier;
wherein the carrier is SiO 2 The Ni particles have an average particle diameter of 10nm or less.
2. SiO according to claim 1 2 A supported Ni catalyst, wherein, in the form of SiO 2 The mass fraction of Ni element is 2-9% based on the total weight of the supported Ni catalyst.
3. Preparation of SiO 2 A method of loading a Ni catalyst, the method comprising the steps of:
s1 SiO is prepared from 2 Mixing with nickel source, and performing impregnation treatment to obtain impregnated SiO 2 ；
S2, soaking the impregnated SiO 2 Mixing 2-methylimidazole with a first solvent, and carrying out contact reaction to obtain a precursor material;
s3, carrying out heat treatment on the precursor material in a reducing atmosphere; wherein the SiO is 2 The particle size of (2) is 200-400nm.
4. The method according to claim 1, wherein in step S1, the SiO 2 The molar ratio of the nickel source to the nickel element is (20-90): 1.
5. the method according to claim 1, wherein in step S1, the nickel source is used in the form of a solution containing a second solvent comprising one or more of water, ethanol, methanol and acetone;
the nickel source comprises one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
in step S2, the first solvent includes one or more of water, ethanol, methanol, acetone, N-dimethylformamide and ammonia water;
optionally, the molar ratio of the nickel source to the 2-methylimidazole, calculated as nickel element, is (0.1-5): 1.
6. the method according to claim 1, wherein in step S1, the conditions of the dipping treatment include: stirring for 8-48h at 20-80deg.C;
in step S2, the conditions of the contact reaction include: stirring for 0.1-48 hr at 50-150deg.C;
in step S3, the heat treatment conditions include: the temperature is 300-900 ℃ and the time is 2-8h.
7. The method of claim 1, wherein step S1 further comprises: the SiO is subjected to 2 Mixing and stirring the solution containing nickel source, carrying out the dipping treatment, carrying out solid-liquid separation on the first reaction material obtained by the reaction, and drying the obtained first solid material to obtain the dipped SiO 2 ；
Step S2 further includes: the impregnated SiO is subjected to 2 Dispersing in the first solvent, adding the 2-methylimidazole into the obtained mixed material, carrying out the contact reaction, carrying out solid-liquid separation on the second reaction material obtained by the reaction, and drying the obtained second solid material to obtain the precursor material;
optionally, the impregnated SiO is based on the volume of the first solvent 2 The dosage of (2) is 0.5-1.5mol/mL;
optionally, in step S3, the reducing atmosphere includes a hydrogen-argon mixture and/or a hydrogen-nitrogen mixture.
8. SiO produced by the method according to any of claims 3 to 7 2 Supported Ni catalyst.
9. SiO as claimed in any of claims 1, 2 and 8 2 The supported Ni catalyst is applied to dicyclopentadiene catalytic hydrogenation reaction.
10. The use of claim 9, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 40-200 ℃, the hydrogen pressure is 0.5-6MPa, the reaction time is 0.2-20h, and the stirring speed is high: 400-1000r/min of the SiO 2 The mass ratio of the supported Ni catalyst to the dicyclopentadiene is 1: (5-20);
optionally, the catalytic hydrogenation reaction is performed in a third solvent, wherein the third solvent is selected from one or more of methylcyclohexane, cyclohexane and n-hexane.
CN202111276375.7A 2021-10-29 2021-10-29 SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof Pending CN116060012A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116571263A (en) * 2023-05-15 2023-08-11 厦门大学 Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116571263A (en) * 2023-05-15 2023-08-11 厦门大学 Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural
CN116571263B (en) * 2023-05-15 2024-05-03 厦门大学 Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of 5-hydroxymethylfurfural

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