CN110882696B - Catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon and preparation method thereof - Google Patents

Catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon and preparation method thereof Download PDF

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CN110882696B
CN110882696B CN201911230102.1A CN201911230102A CN110882696B CN 110882696 B CN110882696 B CN 110882696B CN 201911230102 A CN201911230102 A CN 201911230102A CN 110882696 B CN110882696 B CN 110882696B
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CN110882696A (en
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李向伟
高忠民
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Beijing Sino Sphere Petrochemical Technologies Co ltd
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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • 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 invention relates to a catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon and a preparation method thereof, wherein Pt is used as an active metal component and ZrO is used 2 Is a carrier modifier, and the carrier is alumina containing Ga. Ga in the catalyst provided by the invention 2 O 3 The catalyst is added into an alumina carrier by an in-situ preparation method, and the excellent semiconductor characteristics of the catalyst interact with noble metal Pt, so that the activity of active metal Pt on the catalyst can be effectively improved, and the catalyst is favorable for high activity of aromatic hydrogenation reaction. And ZrO 2 The catalyst has excellent surface chemical property and thermal stability, can obviously reduce the surface acidity of the alumina carrier, can weaken the surface acidity of the carrier, improve the dispersity of Pt on the surface of the carrier, and simultaneously reduce the carbon deposition inactivation of the catalyst in the reaction process, thereby prolonging the activity stability of the catalyst.

Description

Catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for producing cycloalkane by hydrogenation of aromatic hydrocarbon and a preparation method thereof.
Background
Hydrogen energy is a very important renewable energy source, and is currently receiving wide attention at home and abroad. Especially, the research, development and utilization of hydrogen energy in japan are leading in the world. The storage and transportation of hydrogen energy is the key to hydrogen energy utilization, and the method of organic hydrogen compounds (chemical hydrogen storage) is currently the focus of research and has begun to be applied. The chemical hydrogen storage method is to store, transport and release hydrogen by hydrogenation-dehydrogenation reaction of aromatic hydrocarbons such as benzene and toluene. The new generation hydrogen energy industry chain technology research institute is established by combining four companies including Japan thousand generations of field chemical engineering construction, Mitsubishi business, Mitsui products and Japan postal carrier, the methane-cyclohexane hydrogen storage is transported from Wenlai sea to Kawasaki in 2020, and the annual supply scale reaches 210 tons.
The cyclanes as organic liquid hydrogen storage material need to be obtained from hydrogenation reaction of aromatic hydrocarbon (benzene, toluene). The hydrogenation reaction of aromatic hydrocarbon is the main reaction for hydrogen storage, and the core of the hydrogenation reaction of aromatic hydrocarbon is an aromatic hydrocarbon hydrogenation catalyst. The hydrogenation reaction is defined as a process of converting an unsaturated bond into a saturated bond by introducing a hydrogen atom into an unsaturated compound, and can be classified into gas-phase hydrogenation and liquid-phase hydrogenation from the state of the reaction system. Taking benzene hydrogenation as an example, there is often a relatively high requirement on the selectivity of the catalyst during the hydrogenation reaction, and only part of the functional groups need to be hydrogenated according to the product requirement, so as to produce a specific product. Different industrial production methods for preparing cyclohexane by benzene hydrogenation can be combined by different reactor forms, reaction operating conditions and types of catalysts, the isomerization of the cyclohexane is limited, and the generation of byproducts is the key point for controlling the reaction. The method for preparing cyclohexane by benzene hydrogenation can be divided into the following steps according to different reaction conditions: gas phase processes, liquid phase processes, and liquid-gas phase processes. The catalyst adopted in the hydrogenation process is a nickel catalyst or a platinum catalyst, the catalyst is filled in a fixed bed tubular reactor which is continuously operated, the cyclohexane content of the product prepared by the gas phase method is higher than 90 percent, the selectivity of the catalyst to cyclohexane is very high, the reaction of other byproducts hardly occurs, and the catalyst has very high value for wide popularization and use. Liquid phase benzene hydrogenation processes typically employ Raney nickel catalysts, and the reaction is carried out batchwise in a tank reactor. In the liquid-gas phase hydrogenation method, raw materials enter a reactor in a liquid state in the reaction process, and the liquid-phase reaction and the gas-phase reaction can be simultaneously carried out in the continuous operation process, so that the production efficiency is improved, the mass transfer efficiency is greatly improved, and the conversion rate of benzene is relatively high.
In the gas-phase benzene hydrogenation method, a great deal of research is carried out at home and abroad on catalysts for preparing cyclohexane by hydrogenation of platinum-series benzene.
Dombianguez et Al with Al 2 O 3 As a carrier, a platinum-series benzene hydrogenation catalyst is prepared by modifying supported Ga, and the Pt has the best activity at 0.5 percent. [ Dompingeuez F, S-nchez J, artemia G, et al. Gallia as support of Pt in benzene hydrogeneon reaction[J]. J. Mol. Catal. A: Chem., 2005, 228: 319-324.]However, the catalyst prepared by the method has poor benzene hydrogenation stability and cannot be used for a long period.
CN107096533A invented a macroporous alumina carrier as a carrier of platinum-series benzene hydrogenation catalyst, with platinum content of 1.5%, palladium content of 1.5%, benzene removal rate of 100%, and platinum loss rate relatively low. However, the platinum content of the catalyst is high, and the cost of the catalyst is high.
Bimetallic catalysts have also been extensively studied and Lu S L et Al have employed the impregnation method with gamma-Al 2 O 3 Preparing Pt-Co/gamma-Al for carrier 2 O 3 / Pt-Ni/γ-Al 2 O 3 The double metal catalyst has higher benzene hydrogenating activity than single metal catalyst, and the benzene converting rate of the catalyst is up to 60% at 70 deg.c and 1 atm. [ Lu S L, Lonergan W, Bosco J P, et Al, Low temperature hydrolysis of bezene and cyclohexene A reactive tween. gamma. -Al 2 O3 supported Pt-Co and Pt-Ni bimetallic catalysts[J]. J Catal, 2008(259): 260-268.]However, the catalyst is used under mild conditions, and the activity of the catalyst is not high.
In summary, the main problems of the existing catalyst for producing naphthenic hydrocarbon by hydrogenation of aromatic hydrocarbon are that the Pt content of the platinum catalyst is high, the catalyst is expensive, and the activity and stability of the catalyst are poor. To solve this problem, effective modification of the support is critical. The key to the preparation of the catalyst is that the dispersity of Pt on the surface of the carrier is improved, more active phases are promoted to be generated on the surface of the catalyst, the Pt content is reduced, and the activity and the stability of the catalyst are improved.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a catalyst for producing cycloalkane by hydrogenation of aromatic hydrocarbon and a preparation method thereof.
One of the purposes of the invention is to provide a catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon, which takes Pt as an active metal component and takes ZrO 2 Is a carrier modifier, and the carrier is alumina containing Ga. The invention adopts an in-situ preparation method to prepare the Ga-containing alumina oxideAnd the catalyst further takes alumina as a carrier, Zr activity modification is carried out on the surface of the alumina, and then active metal Pt is loaded. Ga 2 O 3 The catalyst is a semiconductor oxide, is added into an alumina carrier by an in-situ preparation method, is more uniformly distributed, has excellent semiconductor characteristics and interacts with noble metal Pt, can effectively improve the activity of active metal Pt on the catalyst, and is beneficial to the high activity of aromatic hydrogenation reaction. And ZrO 2 The catalyst has excellent surface chemical property and good thermal stability, can obviously reduce the surface acidity of the alumina carrier, can weaken the surface acidity of the carrier, improve the dispersity of Pt on the surface of the carrier, and simultaneously reduce the carbon deposition inactivation of the catalyst in the reaction process, thereby prolonging the activity stability of the catalyst.
According to some preferred embodiments of the invention, the alumina support is γ -Al 2 O 3 (ii) a And/or the Ga is Ga 2 O 3 . The catalyst of the invention takes alumina containing Ga as a carrier, Pt as an active metal component and ZrO 2 Is a carrier modifier. Wherein ZrO 2 The dispersion degree of the active metal on the surface of the carrier is improved, and the formation of the active metal component can be promoted.
According to some preferred embodiments of the present invention, the content of Pt is 0.05 to 3.0wt% based on the total weight of the catalyst, and Ga 2 O 3 Is 2.0 to 4.0wt%, ZrO 2 The content of (A) is 0.3-5.0 wt%; preferably, the content of Pt is 0.1-1.0 wt%, and Ga 2 O 3 Is 1 to 3wt% of ZrO 2 The content of (B) is 2.0-4.0 wt%.
According to some preferred embodiments of the present invention, the carrier has an equivalent diameter of 0.2 to 5.0 mm; and/or the specific surface area of the carrier is 180-250 m 2 (ii)/g; and/or the pore volume is 0.41-0.80 ml/g; and/or the density of the carrier is 0.50-0.90 g/cm 3 (ii) a And/or the carrier is strip-shaped; preferably, the equivalent diameter of the carrier is 0.5-2.0 mm, and the specific surface area is 190-230 m 2 Per g, pore volume of 0.5-0.8 ml/g, density of 0.55-0.70 g/cm 3 。
In another aspect, the present invention provides a method for preparing a catalyst for producing cycloalkanes by hydrogenation of aromatics, comprising the following steps:
1) preparing a zirconium-containing alumina carrier: adding the aluminum salt mixed solution, a pH regulator and a gallium trichloride solution into a gel forming tank to form gel, aging, vacuum drying, forming and roasting to obtain Ga 2 O 3 /γ-Al 2 O 3 A carrier; the molding can adopt the technical means commonly used in the field, such as dropping ball molding, extrusion molding and the like;
2) dipping: in the Ga 2 O 3 /γ-Al 2 O 3 Impregnating the carrier with zirconium sulfate, drying and roasting to obtain ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A carrier;
3) impregnation of active metal component: in the ZrO of 2 -Ga 2 O 3 /γ-Al 2 O 3 Dipping the carrier to load chloroplatinic acid, drying and roasting to obtain Pt/ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A catalyst precursor;
4) reduction: and (4) reducing the catalyst precursor obtained in the step (3) to obtain the catalyst. In the invention, in the preparation of the carrier modification, Ga 2 O 3 The catalyst is a semiconductor oxide, is added into an alumina carrier by an in-situ preparation method, is more uniformly distributed, has excellent semiconductor characteristics and interacts with noble metal Pt, can effectively improve the activity of active metal Pt on the catalyst, and is beneficial to the high activity of aromatic hydrogenation reaction. And ZrO 2 The catalyst has excellent surface chemical property and good thermal stability, can obviously reduce the surface acidity of the alumina carrier, can weaken the surface acidity of the carrier, improve the dispersity of Pt on the surface of the carrier, and simultaneously reduce the carbon deposition inactivation of the catalyst in the reaction process, thereby prolonging the activity stability of the catalyst.
According to some preferred embodiments of the present invention, in step 1), the aluminum salt solution uses one or more of aluminum trichloride, aluminum sulfate and aluminum nitrate as a solute, preferably aluminum trichloride, and the concentration of the aluminum salt solution is 0.8 to 1.2M; and/or in the step 1), the pH regulator is ammonia water, preferably, the dosage of the pH regulator is based on the regulation of the pH value of the reaction system to 8-10; and/or, gelling at 60-90 ℃, preferably 70 ℃.
According to some preferred embodiments of the invention, step 1): preparing an aluminum trichloride aqueous solution with the concentration of 0.8-1.2M, adding the aluminum trichloride aqueous solution and an ammonia water solution into a glue forming tank in a parallel flow manner, controlling the flow rate to be 1-3 mL/min, preferably 2.0mL/min, and titrating and adding GaCl at the same time at the flow rate of 1-3 mL/min, preferably 2.0mL/min 3 The temperature of the hot water solution in the gelling tank is controlled to be 70 ℃, and the PH value is 8-10; after the cementing, aging for 0.3-0.8 h, preferably 0.5h, drying at 40-70 ℃ and 50 ℃ for 50-80 h, preferably 60h under vacuum condition, roasting at 500-800 ℃ and preferably 700 ℃ for 4-7 h, preferably 6h under nitrogen atmosphere condition after forming, and obtaining Ga 2 O 3 Ga contained in 2.0-4.0 wt% of alumina carrier 2 O 3 /γ-Al 2 O 3 。
According to some preferred embodiments of the present invention, in step 2) and step 3), the drying is performed at 100-120 ℃ for 2-5 h; the roasting is carried out for 2-5h at 500-800 ℃, preferably 500-700 ℃.
According to some preferred embodiments of the present invention, in the step 3), the reduction temperature is 500-700 ℃, and the reduction pressure is 0.05-0.5 MPa; preferably, hydrogen is used as the reducing agent, and the volume flow rate ratio of hydrogen to the catalyst for reduction per hour is V H2 /V cat Is 1000: 1.
The invention also provides an application of the catalyst in preparation of cycloalkane by hydrogenation of aromatic hydrocarbon, preferably in hydrogenation of aromatic hydrocarbon such as benzene, toluene and xylene.
The invention has the beneficial effects that: the catalyst of the invention takes benzene as raw material, and the space velocity is 10.0h at 120 DEG C -1 When the pressure was 3.0MPa and the hydrogen-oil molar ratio after subtracting the chemical hydrogen consumption was 1.0, the conversion of aromatics after 30 days was evaluated as 100%. The results show that the catalyst of the invention has outstanding aromatic hydrocarbon hydrogenation capability and improves the activity and stability of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The technical solution of the present invention is not limited to the following specific embodiments, and includes any combination of the specific embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the present invention, the specific techniques or conditions not specified in the examples are performed according to the techniques or conditions described in the literature in the art or according to the product specification. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets.
Example 1
The catalyst of the invention takes alumina containing Ga as a carrier, Pt as an active metal component and ZrO as ZrO 2 Is a carrier modifier. Pt content 0.3wt%, based on the weight of the catalyst, ZrO 2 Content of (1.5 wt.%), Ga 2 O 3 The content of (B) was 2.5 wt%.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
the method comprises the following steps: preparation of zirconium-containing alumina carrier
Preparing 0.98M aluminum trichloride solution, slowly adding the aluminum trichloride solution and ammonia water solution in a cocurrent manner into a gelling tank, and simultaneously titrating and adding gallium trichloride GaCl 3 The flow rate of the aluminum trichloride is 2.0ml/min, and the flow rate of the gallium trichloride is GaCl 3 The hot water solution is added in a titration manner at the flow rate of 2.0ml/min, the temperature in a gelling tank is controlled to be 70 ℃, and the PH value is 8.0-10.0. Aging for 0.5h after the cementing, drying for 60h at 50 ℃ under the vacuum condition, roasting for 6h at 700 ℃ under the nitrogen atmosphere after molding, and obtaining the Ga-containing material 2 O 3 Ga on alumina carrier of 2.5wt% 2 O 3 /γ-Al 2 O 3 。
Step two: impregnation
In 80-120 parts by weight of Ga 2 O 3 /γ-Al 2 O 3 Dipping a zirconium sulfate solution on a carrier, drying the dipped product for 2-5 hours at the temperature of 100-120 ℃, and then roasting the product for 2-5 hours in a muffle furnace at the temperature of 500-700 ℃ to obtain ZrO 2 ZrO in an amount of 1.5wt% based on the final catalyst 2 -Ga 2 O 3 /γ-Al 2 O 3 A carrier;
step three: active metal impregnation
80-120 parts by weight of ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 Dipping a chloroplatinic acid solution on a carrier, drying the dipped product for 2-5 hours at the temperature of 100-120 ℃, and then roasting the product for 2-5 hours in a muffle furnace at the temperature of 500-700 ℃ to obtain Pt/ZrO with the Pt content of 0.3wt0% 2 -Ga 2 O 3 /γ-Al 2 O 3 A catalyst;
step four: reduction of
Reducing the product obtained in the third step at 200-500 ℃ for 2-5h under the reduction pressure of 1-3 MPa, wherein the volume flow rate ratio of hydrogen to the catalyst per hour is V H2 /V cat The ratio is 1000:1, and then the temperature of the catalyst is reduced.
Example 2
The catalyst of the invention takes alumina containing Ga as a carrier, Pt as an active metal component and ZrO as ZrO 2 Is a carrier modifier. Pt content 0.35wt%, based on the weight of the catalyst, ZrO 2 Content of (2.0 wt.%), Ga 2 O 3 The content of (B) was 2.5 wt%.
This example also provides the preparation of the catalyst described above, which is the same as example 1.
Example 3
The catalyst for hydrogenation of arene to produce cyclane contains Ga, taking alumina as a carrier, taking Pt as an active metal component and taking ZrO 2 Is a carrier modifier. Pt content 0.4wt%, based on the weight of the catalyst, ZrO 2 Content of (2.5 wt.%), Ga 2 O 3 The content of (B) was 2.5 wt%.
This example also provides a method for preparing the catalyst, which is the same as example 1.
Comparative example 1
A catalyst for the hydrogenation of aromatics to produce naphthenes, prepared according to the method of example 1, containing 0.3% Pt, but containing no Ga on the support and no ZrO on the support 2 。
Evaluation of Effect
The evaluation method comprises the following steps: on a fixed bed reactor, adopting the catalysts of examples 1-3 and comparative example 1, and carrying out a reaction for preparing cyclohexane by hydrogenation with benzene as a raw material, wherein the dosage of the catalyst is 100ml, and the volume space velocity of the benzene is 10.0h -1 The catalyst was continuously evaluated under the above reaction conditions for 30 days under the reaction pressure of 3.0MPa, the reaction temperature of 120 ℃ and the hydrogen-oil molar ratio after subtraction of chemical hydrogen consumption of 1.0.
Evaluation results were as follows: the results are shown in Table 1.
Figure 797416DEST_PATH_IMAGE001
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (12)

1. A catalyst for preparing cyclic alkane by hydrogenating aromatic hydrocarbon features that Pt is used as active metal component and ZrO is used 2 Is a carrier modifier, and the carrier is alumina containing Ga; the catalyst for producing naphthenes by hydrogenation of aromatics is prepared by the method comprising the following steps:
1) preparing a zirconium-containing alumina carrier: adding the aluminum salt solution, a pH regulator and a gallium trichloride solution into a gel forming tank, forming gel, aging, vacuum drying, forming and roasting to obtain Ga 2 O 3 /γ-Al 2 O 3 A carrier;
2) dipping: in the Ga 2 O 3 /γ-Al 2 O 3 Impregnating the carrier with zirconium sulfate, drying and roasting to obtain ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A carrier;
3) impregnation of active metal component: in the presence of the ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 Dipping the carrier to load chloroplatinic acid, drying and roasting to obtain Pt/ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A catalyst precursor;
4) reduction: and (4) reducing the catalyst precursor obtained in the step (3) to obtain the catalyst.
2. The catalyst according to claim 1, wherein the content of Pt is 0.05-3.0 wt% based on the total weight of the catalyst, and Ga 2 O 3 The content of (b) is 2.0-4.0 wt%, ZrO 2 The content of (b) is 0.3-5.0 wt%.
3. The catalyst according to claim 2, wherein the content of Pt is 0.1-1.0 wt%, Ga 2 O 3 Is 1 to 3wt% of ZrO 2 The content of (B) is 2.0-4.0 wt%.
4. The catalyst according to any one of claims 1 to 3, wherein the carrier has an equivalent diameter of 0.2 to 5.0 mm; and/or the specific surface area of the carrier is 180-250 m 2 (iv) g; and/or the pore volume is 0.41-0.80 ml/g; and/or the density of the carrier is 0.50-0.90 g/cm 3 (ii) a And/or the carrier is strip-shaped.
5. The catalyst according to claim 4,the equivalent diameter of the carrier is 0.5-2.0 mm, and the specific surface area is 190-230 m 2 A pore volume of 0.5 to 0.8ml/g and a density of 0.55 to 0.70g/cm 3 。
6. A preparation method of the catalyst for producing cycloalkane by hydrogenation of aromatic hydrocarbon according to any one of claims 1 to 5, comprising the steps of:
1) preparing a zirconium-containing alumina carrier: adding the aluminum salt solution, a pH regulator and a gallium trichloride solution into a gel forming tank, forming gel, aging, vacuum drying, forming and roasting to obtain Ga 2 O 3 /γ-Al 2 O 3 A carrier;
2) dipping: in the Ga 2 O 3 /γ-Al 2 O 3 Impregnating the carrier with zirconium sulfate, drying and roasting to obtain ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A carrier;
3) impregnation of active metal component: in the ZrO of 2 -Ga 2 O 3 /γ-Al 2 O 3 Dipping the carrier to load chloroplatinic acid, drying and roasting to obtain Pt/ZrO 2 -Ga 2 O 3 /γ-Al 2 O 3 A catalyst precursor;
4) reduction: and (4) reducing the catalyst precursor obtained in the step (3) to obtain the catalyst.
7. The method as claimed in claim 6, wherein in the step 1), the aluminum salt solution takes one or more of aluminum trichloride, aluminum sulfate and aluminum nitrate as a solute; and/or, in the step 1), the pH regulator is ammonia water; and/or, gelling at the temperature of 60-90 ℃.
8. The method according to claim 7, wherein in step 1), the aluminum salt solution is aluminum trichloride; and/or in the step 1), the dosage of the pH regulator is based on the regulation of the pH value of the reaction system to 8-10.
9. According to claim6, characterized in that step 1): preparing an aluminum trichloride aqueous solution with the concentration of 0.8-1.2M, adding the aluminum trichloride aqueous solution and an ammonia water solution into a glue forming tank in a parallel flow manner, controlling the flow rate to be 1-3 mL/min, and simultaneously titrating and adding GaCl at the flow rate of 1-3 mL/min 3 The temperature of the hot water solution in the gelling tank is controlled to be 70 ℃, and the pH value is 8-10; after the cementing, aging for 0.3-0.8 h, drying for 50-80 h at 40-70 ℃ under a vacuum condition, roasting for 4-7 h at 500-800 ℃ under a nitrogen atmosphere after forming, and obtaining Ga 2 O 3 Ga contained in an alumina carrier of 2.0-4.0 wt% 2 O 3 /γ-Al 2 O 3 。
10. The method according to claim 6, wherein in the step 2) and the step 3), the drying is carried out at 100-120 ℃ for 2-5 h; the roasting is carried out for 4-7 h at 500-800 ℃.
11. The method according to any one of claims 6 to 10, wherein in the step 4), the reduction temperature is 500 to 700 ℃ and the reduction pressure is 0.05 to 0.5 MPa.
12. The process of claim 11, wherein hydrogen is used as the reducing agent and the volume flow rate ratio of hydrogen to catalyst per hour for reduction is V H2 /V cat Is 1000: 1.
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