A SiO2-supported Ni catalyst and its preparation method and application
Through the preparation of SiO2-supported Ni catalyst, the problems of low activity and poor stability of existing catalysts in DCPD hydrogenation reaction were solved, and efficient catalysis of dicyclopentadiene was achieved. The raw material selectivity and product selectivity of the hydrogenation reaction were significantly improved, and the stability and economicality of the catalyst were also improved.
Patent Information
- Application Number
- CN202111276375.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-10-29
- Publication Date
- 2025-03-11
- Estimated Expiration
- 2041-10-29
AI Technical Summary
The existing catalysts have problems of low activity and poor stability in DCPD hydrogenation reaction, and precious metal catalysts are expensive, and non-precious metal nickel-based catalysts are insufficient in activity and stability.
A SiO2-supported Ni catalyst was developed, and prepared by impregnation treatment, contact reaction and heat treatment of SiO2 and nickel source, so as to ensure that the average particle size of Ni particles is below 10 nm and improve catalytic activity and stability.
High-efficiency catalytic hydrogenation of dicyclopentadiene is achieved, high raw material selectivity and bridge tetrahydrodicyclopentadiene selectivity, reducing the amount of Ni, and improving the stability and economicality of the catalyst.
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Figure CN116060012B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of petrochemical technology, and in particular to a SiO 2 Supported Ni catalyst and preparation method and application thereof. Background Art
[0002] With the increasing scale of ethylene and petroleum catalytic cracking units, C5 fraction resources are becoming increasingly abundant. As the most important fraction separated from C5, how to digest and apply dicyclopentadiene (DCPD) has become a hot topic in the petrochemical field. DCPD can be hydrogenated to produce tetrahydrodicyclopentadiene (endo-THDCPD). Endo-THDCPD is a solid fuel with high energy density. It is also an intermediate for the synthetic fuel tetrahydrodicyclopentadiene and an intermediate for the synthesis of adamantane, a fine chemical raw material with extremely high added value.
[0003] At present, the Raney nickel catalyst that has been put into industrial use has a high DCPD hydrogenation activity, but the catalyst is easy to be natural in the air, difficult to store, has a short service life, and is not easy to regenerate. In addition, most of the catalysts with good DCPD hydrogenation activity are precious metals, but due to their high price and limited sources, their application is subject to certain restrictions. The non-precious metal nickel-based catalysts reported so far have the problems of low activity and poor stability. Therefore, the present invention intends to develop a new non-precious metal catalyst to achieve efficient catalytic hydrogenation of dicyclopentadiene. Summary of the invention
[0004] The purpose of the present invention is to provide a SiO 2 Supported Ni catalyst and preparation method and application thereof, the SiO 2 The average particle size of Ni particles in the supported Ni catalyst is small and has excellent hydrogenation performance. When it is applied to the hydrogenation reaction of dicyclopentadiene, higher raw material selectivity and selectivity of bridged tetrahydrodicyclopentadiene can be obtained.
[0005] In order to achieve the above-mentioned object, the present disclosure first provides SiO 2 The supported Ni catalyst, the SiO 2 The supported Ni catalyst includes a carrier and Ni particles supported on the carrier;
[0006] Wherein, the carrier is SiO 2 , the average particle size of the Ni particles is less than 10 nm.
[0007] Optionally, the SiO 2 The total weight of the supported Ni catalyst is taken as a reference, and the mass fraction of the Ni element is 2-9% in terms of mass fraction.
[0008] The second aspect of the present disclosure provides a method for preparing SiO2 A method for preparing a supported Ni catalyst, the method comprising the following steps:
[0009] S1SiO 2 Mixed with nickel source, impregnated to obtain impregnated SiO 2 ;
[0010] S2: the impregnated SiO 2 , 2-methylimidazole is mixed with the first solvent to carry out a contact reaction to obtain a precursor material;
[0011] S3 heat-treating the precursor material in a reducing atmosphere;
[0012] Wherein, the SiO 2 The particle size is 200-400nm.
[0013] Optionally, in step S1, the SiO 2 The molar ratio of the nickel source calculated as nickel element is (20-90):1.
[0014] Optionally, the nickel source is used in the form of a solution, the solution contains a second solvent, and the second solvent includes one or more of water, ethanol, methanol and acetone;
[0015] The nickel source includes one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
[0016] In step S2, the first solvent includes one or more of water, ethanol, methanol, acetone, N,N-dimethylformamide and ammonia;
[0017] Optionally, the molar ratio of the nickel source to the 2-methylimidazole is (0.1-5):1, calculated as nickel element.
[0018] Optionally, the conditions for the immersion treatment include: carrying out the treatment under stirring for 8-48 hours at a temperature of 20-80°C;
[0019] In step S2, the contact reaction conditions include: carrying out under stirring conditions, the time is 0.1-48h, and the temperature is 50-150°C;
[0020] In step S3, the heat treatment conditions include: temperature of 300-900° C. and time of 2-8 hours.
[0021] Optionally, step S1 further comprises: 2 The solution containing the nickel source is mixed and stirred to perform the impregnation treatment, the first reaction material obtained by the reaction is subjected to solid-liquid separation, and the first solid material obtained is dried to obtain the impregnated SiO2 ;
[0022] Step S2 also includes: 2 Dispersing in the first solvent, adding the 2-methylimidazole to the obtained mixed material, performing the 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;
[0023] Optionally, based on the volume of the first solvent, the impregnated SiO 2 The dosage is 0.5-1.5 mol / mL;
[0024] Optionally, in step S3, the reducing atmosphere includes a hydrogen-argon mixture and / or a hydrogen-nitrogen mixture.
[0025] The third aspect of the present disclosure provides a SiO prepared by the method described in the second aspect of the present disclosure. 2 Supported Ni catalyst.
[0026] In a fourth aspect, the present disclosure provides the SiO 2 Application of supported Ni catalyst in catalytic hydrogenation of dicyclopentadiene.
[0027] Optionally, the conditions of the catalytic reaction include: reaction temperature of 40-200°C, hydrogen pressure of 0.5-6MPa, reaction time of 0.2-20h, stirring speed of 400-1000r / min, the SiO 2 The mass ratio of the supported Ni catalyst to the dicyclopentadiene is 1:(5-20);
[0028] Optionally, the catalytic hydrogenation reaction is carried out in a third solvent, and the third solvent is selected from one or more of methylcyclohexane, cyclohexane and n-hexane.
[0029] Through the above technical solution, this application will use SiO 2 The precursor material of the Ni MOFs material is subjected to heat treatment to obtain SiO 2 The method for preparing a supported Ni catalyst can avoid the aggregation of the active component nickel in the prepared catalyst, achieve uniform distribution of the active component, and the average particle size of the Ni particles in the catalyst is below 10 nm, so that the catalyst has an excellent catalytic effect and can reduce the amount of Ni used. When used in the catalytic hydrogenation reaction of dicyclopentadiene, a higher raw material conversion rate and selectivity for bridged tetrahydrodicyclopentadiene can be obtained.
[0030] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:
[0032] Figure 1 The SiO prepared in Example 1 2 XRD diffraction pattern of supported Ni catalyst A1.
[0033] Figure 2 The SiO prepared in Example 1 2 SEM image of supported Ni catalyst A1.
[0034] Figure 3 The SiO prepared in Example 1 2 HRTEM image of supported Ni catalyst A1.
[0035] Figure 4 It is the infrared spectra of the precursor material and Ni ZIF prepared in Example 1. DETAILED DESCRIPTION
[0036] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.
[0037] The present invention provides a SiO 2 The supported Ni catalyst, the SiO 2 The supported Ni catalyst includes a support and Ni particles supported on the support;
[0038] Wherein, the carrier is SiO 2 , the average particle size of the Ni particles is less than 10 nm.
[0039] In a preferred embodiment of the present disclosure, the average particle size of the Ni particles is 5-10 nm. The Ni particles contain single-element Ni, and preferably all Ni elements exist in single-element form.
[0040] In one embodiment of the present disclosure, SiO 2 The total weight of the loaded Ni catalyst is taken as the reference, and the mass fraction of the Ni element is 2-9%, preferably 2-5%. 2 When the loaded Ni catalyst is used in the catalytic hydrogenation reaction of dicyclopentadiene, it can effectively improve the conversion rate of the raw material and the selectivity of bridged tetrahydrodicyclopentadiene under the premise of lower nickel loading, thereby obtaining a better catalytic effect.
[0041] The second aspect of the present disclosure provides a method for preparing SiO 2 A method for preparing a supported Ni catalyst, the method comprising the following steps:
[0042] S1SiO 2 Mixed with nickel source, impregnated to obtain impregnated SiO 2 ;
[0043] S2: the impregnated SiO 2 , 2-methylimidazole is mixed with the first solvent to carry out a contact reaction to obtain a precursor material;
[0044] S3 heat-treating the precursor material in a reducing atmosphere;
[0045] Wherein, the SiO 2 The particle size is 200-400nm.
[0046] SiO that meets the above average particle size range 2 The problem of poor loading effect caused by too large or too small particle size is avoided. 2 The Ni particles in the prepared catalyst can have a smaller particle size, which is beneficial to improving the catalytic performance.
[0047] In one embodiment of the present disclosure, in step S3, the reducing atmosphere includes a hydrogen-argon mixture and / or a hydrogen-nitrogen mixture. The volume ratio of hydrogen to nitrogen in the hydrogen-nitrogen mixture is 1:(0.5-2), and the volume ratio of hydrogen to argon in the hydrogen-argon mixture is 1:(0.5-2). Specifically, the reducing atmosphere can be a hydrogen-nitrogen mixture with a volume ratio of 1:1.
[0048] In the present disclosure, step S2 is to convert SiO 2 The carrier and Ni MOFs material are composited and SiO is obtained after heat treatment in step S3. 2 The method can reduce the aggregation degree of the active component Ni in the supported Ni catalyst, so that the average particle size of the Ni particles is below 10 nm, thereby obtaining a higher dispersion of the active metal.
[0049] In one embodiment of the present disclosure, in step S1, SiO 2 The molar ratio of the nickel source calculated as nickel element is (20-90):1, preferably (20-60):1.
[0050] In the present disclosure, the SiO used in step S1 2 The following methods can be used for preparation:
[0051] The silicon source is mixed with the fourth solvent, reacted, and SiO is obtained through solid-liquid separation and drying. 2 . The silicon source includes tetraethyl orthosilicate and / or silica sol, for example, tetraethyl orthosilicate. The fourth solvent includes one or more of water, ethanol, methanol and acetone, preferably a mixture of water and ethanol. Among them, the volume ratio of water to ethanol is (0.1-8):1, preferably (0.1-4):1; 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 in terms of 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°C; preferably, the time is 5-12h, and the temperature is 20-50°C. SiO prepared by the above method 2 The particle size is 200-400nm.
[0052] In one embodiment of the present disclosure, the molar ratio of the silicon source calculated as silicon element to the nickel source calculated as nickel element is (1-30):1, preferably (1-20):1.
[0053] In one embodiment of the present disclosure, in step S1, the nickel source is used in the form of a solution, and the solution contains a second solvent, and the second solvent includes one or more of water, ethanol, methanol and acetone; for example, it can be water.
[0054] In one embodiment of the present disclosure, the nickel source includes 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.
[0055] In one embodiment of the present disclosure, in step S2, the first solvent includes one or more of water, ethanol, methanol, acetone, N,N-dimethylformamide and ammonia water; preferably includes one or more of water, ethanol, methanol, acetone and N,N-dimethylformamide; for example, it can be methanol.
[0056] In one embodiment of the present disclosure, the molar ratio of the nickel source calculated as nickel element to 2-methylimidazole is (0.1-5):1, preferably (0.1-3):1.
[0057] In one embodiment of the present disclosure, in step S1, the conditions for the immersion treatment include: the immersion treatment is carried out under stirring, the time is 8-48 hours, and the temperature is 20-80°C; preferably, the time is 8-24 hours, and the temperature is 20-60°C.
[0058] In one embodiment of the present disclosure, in step S2, the contact reaction conditions include: under stirring, the time is 0.1-72 hours, the temperature is 50-150° C.; preferably, the time is 0.1-24 hours, and the temperature is 50-100° C. In another embodiment, stirring is first performed for 10-30 minutes without heating, and then heating is turned on to continue stirring.
[0059] In the present disclosure, the stirring method is conventional in the art, for example, it can be magnetic stirring.
[0060] In step S3, the heat treatment conditions include: temperature of 300-900°C, time of 2-8h; preferably, temperature of 400-800°C, time of 2-5h. Meeting the above heat treatment conditions can ensure that the Ni MOF material is fully pyrolyzed to obtain active metal Ni particles.
[0061] In one embodiment of the present disclosure, step S1 further includes: 2 The solution containing the nickel source is mixed and stirred, and an impregnation treatment is performed to separate the first reaction material obtained by the reaction into solid and liquid, and the first solid material obtained is dried to obtain the impregnated SiO 2 .
[0062] In one embodiment of the present disclosure, step S2 further includes: 2 The mixture is dispersed in the first solvent, 2-methylimidazole is added to the obtained mixture to carry out a contact reaction, the second reaction material obtained by the reaction is subjected to solid-liquid separation, and the obtained second solid material is dried to obtain a precursor material.
[0063] In one embodiment of the present disclosure, based on the volume of the first solvent, the impregnated SiO 2 The dosage is 0.5-1.5 mol / mL, preferably 1-1.5 mol / mL.
[0064] In the present disclosure, the drying method is conventional in the art, for example, it can be heating drying.
[0065] The third aspect of the present disclosure provides a SiO prepared by the method described in the second aspect of the present disclosure. 2 Supported Ni catalyst.
[0066] The third aspect of the present disclosure provides SiO 2 The supported Ni catalyst and the SiO 2 The supported Ni catalysts have the same structure and properties.
[0067] In a fourth aspect, the present disclosure provides the SiO 2Application of supported Ni catalyst in catalytic hydrogenation of dicyclopentadiene.
[0068] In one embodiment of the present disclosure, the conditions for the catalytic reaction include: a reaction temperature of 40-200°C, a hydrogen pressure of 0.5-6 MPa, a reaction time of 0.2-20 h, and a SiO 2 The mass ratio of the supported Ni catalyst to dicyclopentadiene is 1:(5-20); preferably, the reaction temperature is 40-140°C, the hydrogen pressure is 0.5-5MPa, the reaction time is 0.5-12h, and SiO 2 The mass ratio of the supported Ni catalyst to dicyclopentadiene is 1:(5-15). Dicyclopentadiene is conventional in the art and no special requirements are made. For example, it can be dicyclopentadiene with a purity of 85-99%.
[0069] In the present disclosure, the stirring speed of the catalytic hydrogenation reaction may be 400-1000 r / min, preferably 400-800 r / min.
[0070] In one embodiment of the present disclosure, the catalytic hydrogenation reaction is carried out in a third solvent, and the third solvent is selected from one or more of methylcyclohexane, cyclohexane and n-hexane, for example, methylcyclohexane.
[0071] The following examples further illustrate the SiO 2 Supported Ni catalyst and its application in catalytic hydrogenation of dicyclopentadiene. The raw materials used in the examples can be obtained through commercial sources.
[0072] The instrument model of XRD diffraction is Panalytical.
[0073] The instrument model for ICP testing is: Agilent ICPOES730.
[0074] The instrument model for infrared spectrum testing is: Nicolet 6700.
[0075] The instrument model for HRTEM testing is: JEM-2100.
[0076] The instrument model for SEM testing is: FESEM, SU-70.
[0077] The test method for the average particle size of the metal Ni particles is: observing and counting the metal particle size under a TEM electron microscope, and the TEM instrument model is JEM-2100.
[0078] In the present application, the conversion rate of dicyclopentadiene and the selectivity of bridged tetrahydrodicyclopentadiene are calculated by gas chromatography using a peak area normalization method, wherein the gas chromatograph model is an Agilent gas chromatograph 7890B.
[0079] Conversion rate = (1-dicyclopentadiene peak area percentage) * 100%
[0080]
[0081] 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.
[0082] Example 1
[0083] The following steps are used to prepare the SiO 2 Supported Ni catalyst.
[0084] (1) Prepare a mixed solution of ethanol and water, then add ethyl orthosilicate and ammonia water, stir at 25°C for 6 hours, and centrifuge to obtain SiO 2 The particle size is 300nm. The test method is: observation and statistics under TEM electron microscope, the TEM instrument model is JEM-2100.
[0085] (2) The SiO obtained in step (1) 2 The mixture was mixed with nickel nitrate solution and stirred at 45 °C for 6 h, and then dried to obtain the impregnated SiO 2 .
[0086] (3) The impregnated SiO 2 The mixture was mixed with methanol and 2-methylimidazole, stirred at 70° C. for 1 h, and then centrifuged and dried to obtain a precursor material.
[0087] (4) The precursor material was heat treated at 500°C for 4 h in a hydrogen and nitrogen mixed gas to obtain SiO 2 The supported Ni / C particle catalyst is denoted as Catalyst A1.
[0088] Figure 1 The SiO prepared in Example 1 2 XRD diffraction pattern of supported Ni catalyst A1.
[0089] Figure 2 The SiO prepared in Example 1 2 SEM image of supported Ni catalyst A1 shows that SiO 2 Ni particles are uniformly grown on the particles.
[0090] Figure 3 The SiO prepared in Example 1 2The HRTEM image of the supported Ni catalyst A1 shows that the interplanar spacing of the small particles is 2.01 Å, corresponding to the (111) crystal plane of metallic Ni, proving that SiO 2 The particles grown on the support are Ni particles.
[0091] The precursor material and Ni ZIF prepared in Example 1 were tested by infrared spectrum. The results are as follows: Figure 4 , ZIF characteristic peaks appeared in the precursor, among which 1430cm -1 The peak is attributed to the skeleton vibration of 2-methylimidazole, proving that the precursor material has a ZIF structure.
[0092] The above catalyst A1 was used in a high pressure reactor to carry out catalytic hydrogenation of dicyclopentadiene (DCPD), the solvent was methylcyclohexane, the mass fraction of dicyclopentadiene was 10%, the mass ratio of catalyst A1 to dicyclopentadiene was 1:10, the reaction temperature was 90°C, the hydrogen pressure was 3MPa, the reaction time was 1h, and the stirring speed was 600r / min. The raw material conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1. The mass fraction of Ni element was tested by ICP.
[0093] The volume ratio of water to ethanol is 0.27:1; the volume ratio of water to ammonia is 3.75:1; the ratio of silicon source to the total volume of ethanol and water is 0.043:1; SiO 2 The molar ratio of the nickel source calculated as nickel element is 60:1; the molar ratio of the nickel source calculated as nickel element to 2-methylimidazole is 0.23:1. Based on the volume of methanol, the impregnated SiO 2 The dosage is 1.3 mol / mL; the volume ratio of hydrogen and nitrogen in the hydrogen-nitrogen mixture is 1:1.
[0094] Example 2
[0095] Catalyst A2 was prepared by the method of Example 1, except that the heat treatment temperature in step (4) was 550° C. and the time was 6 h.
[0096] The above catalyst A2 was used in a high pressure reactor to carry out catalytic hydrogenation of dicyclopentadiene (DCPD), the solvent was methylcyclohexane, the mass fraction of dicyclopentadiene was 10%, the mass ratio of catalyst A2 to dicyclopentadiene was 1:8, the reaction temperature was 90°C, the hydrogen pressure was 3MPa, the reaction time was 3h, and the stirring speed was 600r / min. The raw material conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1.
[0097] The volume ratio of water to ethanol is 0.27:1; the volume ratio of water to ammonia is 3.75:1; the ratio of silicon source to the total volume of ethanol and water is 0.043:1; SiO 2 The molar ratio of the nickel source calculated as nickel element is 60:1; the molar ratio of the nickel source calculated as nickel element to 2-methylimidazole is 0.23:1.
[0098] Example 3
[0099] Catalyst A3 was prepared by the method of Example 1, except that SiO 2 The molar ratio of the nickel source calculated as nickel element is 40:1; the molar ratio of the nickel source calculated as nickel element to 2-methylimidazole is 0.2:1.
[0100] The above catalyst A3 was used in a high pressure reactor to carry out catalytic hydrogenation of dicyclopentadiene (DCPD), the solvent was methylcyclohexane, the mass fraction of dicyclopentadiene was 10%, the mass ratio of catalyst A3 to dicyclopentadiene was 1:8, the reaction temperature was 90°C, the hydrogen pressure was 3MPa, the reaction time was 3h, and the stirring speed was 600r / min. The raw material conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1.
[0101] Example 4
[0102] 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 reaction of dicyclopentadiene, and the reaction conditions were the same as those of Example 1. The feedstock conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1.
[0103] Comparative Example 1
[0104] Synthesize SiO according to Example 1 2 Then, Ni was loaded on SiO by conventional wet impregnation method. 2 Then, conventional air calcination (heating at 450℃ for 3h) and hydrogen reduction (heating at 450℃ for 2h) were used to obtain SiO 2 The supported Ni catalyst is denoted as D1. Catalyst D1 was used for the catalytic hydrogenation reaction of dicyclopentadiene, and the reaction conditions were the same as those in Example 1. The feedstock conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1.
[0105] Comparative Example 2
[0106] Catalyst D2 was prepared by the method of Example 1, except that the SiO 2, nickel nitrate solution, methanol and 2-methylimidazole were mixed and stirred at 70°C for 1 hour, and then centrifuged and dried. The dried solid was heat treated at 500°C for 4 hours in a hydrogen and nitrogen mixture to obtain catalyst D2.
[0107] Catalyst D2 was used for the catalytic hydrogenation of dicyclopentadiene, and the reaction conditions were the same as those in Example 1. The feedstock conversion rate, product selectivity, mass fraction of Ni element, and average particle size of metal Ni particles are listed in Table 1.
[0108] Comparative Example 3
[0109] Catalyst D3 was prepared by the method of Example 1, except that commercial SiO 2 (20 nm) as a carrier. Catalyst D3 was used for the catalytic hydrogenation of dicyclopentadiene, and the reaction conditions were the same as those in Example 1. The feedstock conversion rate, product selectivity, mass fraction of Ni element and average particle size of metal Ni particles are listed in Table 1.
[0110] Table 1
[0111]
[0112]
[0113] According to the data in Table 1, this application will use SiO 2 The precursor material of the Ni MOFs material is prepared by heat treatment of SiO 2 The supported Ni catalyst, wherein the average particle size of the Ni particles in the catalyst prepared by the above method is below 10 nm, has excellent catalytic performance, and when it is applied to the catalytic hydrogenation reaction of dicyclopentadiene, a higher raw material conversion rate and selectivity of bridged tetrahydrodicyclopentadiene can be obtained.
[0114] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
[0115] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.
[0116] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.
Claims
1. A method for preparing a SiO2-supported Ni catalyst, characterized in that: The method comprises the following steps: S1: mixing SiO2 with a nickel source, and performing an impregnation treatment to obtain impregnated SiO2; S2: mixing the impregnated SiO2 and 2-methylimidazole with the first solvent to carry out a contact reaction to obtain a precursor material; S3 heat-treating the precursor material in a reducing atmosphere; wherein the particle size of the SiO2 is 200-400 nm; In the SiO2-supported Ni catalyst, the average particle size of Ni particles is less than 10 nm; Based on the total weight of the SiO2-loaded Ni catalyst, the mass fraction of the Ni element is 2-9% by mass.
2. The method according to claim 1, wherein: In step S1, the molar ratio of the SiO2 to the nickel source calculated as nickel element is (20-90):
1.
3. The method according to claim 1, wherein: In step S1, the nickel source is used in the form of a solution, the solution contains a second solvent, and the second solvent includes one or more of water, ethanol, methanol and acetone; The nickel source includes 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,N-dimethylformamide and ammonia.
4. The method according to claim 3, wherein: The molar ratio of the nickel source to the 2-methylimidazole is (0.1-5):1, calculated as nickel element.
5. The method according to claim 1, wherein: In step S1, the conditions of the immersion treatment include: carrying out the treatment under stirring for 8-48 hours at a temperature of 20-80°C; In step S2, the contact reaction conditions include: carrying out under stirring conditions, the time is 0.1-48h, and the temperature is 50-150°C; In step S3, the heat treatment conditions include: temperature of 300-900° C. and time of 2-8 h.
6. The method according to claim 1, wherein: Step S1 also includes: mixing and stirring the SiO2 with a solution containing a nickel source, performing the impregnation treatment, performing solid-liquid separation on the first reaction material obtained by the reaction, and drying the obtained first solid material to obtain the impregnated SiO2; Step S2 also includes: dispersing the impregnated SiO2 in the first solvent, adding the 2-methylimidazole to the obtained mixture, performing the 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.
7. The method according to claim 1, wherein: Based on the volume of the first solvent, the amount of SiO2 after the impregnation is 0.5-1.5 mol / mL.
8. The method according to claim 1, wherein: In step S3, the reducing atmosphere includes a hydrogen-argon mixed gas and / or a hydrogen-nitrogen mixed gas.
9. A SiO2-supported Ni catalyst prepared by the method described in any one of claims 1 to 8.
10. Use of the SiO2-supported Ni catalyst according to claim 9 in the catalytic hydrogenation reaction of dicyclopentadiene.
11. The use according to claim 10, wherein: The conditions of the catalytic hydrogenation reaction include: reaction temperature of 40-200°C, hydrogen pressure of 0.5-6 MPa, reaction time of 0.2-20 h, stirring speed of 400-1000 r / min, and a mass ratio of the SiO2-supported Ni catalyst to the dicyclopentadiene of 1:(5-20).
12. The use according to claim 11, wherein: The catalytic hydrogenation reaction is carried out in a third solvent, and the third solvent is selected from one or more of methylcyclohexane, cyclohexane and n-hexane.