A carbon three carbon four total hydrogenation catalyst, a preparation method and application thereof

Abstract

The application provides a carbon three carbon four full hydrogenation catalyst and a preparation method and application thereof, and can fully hydrogenate unsaturated hydrocarbons in a carbon three carbon four fraction generated by a light material cracking device to be saturated. The catalyst comprises a main active component, an auxiliary active component and a carrier. The application controls the distribution of the metal active component by regulating the type, quantity and density of the oxygen-containing groups of the carrier, so as to improve the conversion rate of the unsaturated hydrocarbons.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to a carbon three and carbon four full hydrogenation catalyst as well as a preparation method and application thereof. BACKGROUND

[0002] Petroleum chemical industry is an important industry related to national economy and people's livelihood, and an ethylene device is a production device of various organic chemical raw materials. At present, the raw materials used in the ethylene device at home and abroad mainly include naphtha, ethane, propane, butane, diesel oil, coal and the like. Compared with the traditional naphtha cracking, the light raw material can improve the ethylene yield, reduce the energy consumption and improve the economic benefit of enterprises. In addition to the main product ethylene, the cracking device using the light raw material produces hydrogen, methane, carbon three, carbon four and benzene and toluene and the like. The unsaturated carbon three and carbon four mainly include propylene, propyne (MA), propadiene (PD), butadiene and butene, and the cost of selecting hydrogenation after separation is relatively high, and the mixture is usually fully hydrogenated and then transported to a cracking furnace for use as a cracking raw material.

[0003] The existing technical solution mainly hydrogenates the carbon three or carbon four two kinds of fractions respectively, or the carbon three and carbon four two kinds of hydrogenation catalysts are layered and filled in the hydrogenation reactor of the mixture flow. Therefore, a full hydrogenation catalyst suitable for the mixed carbon three and carbon four fractions generated by the light raw material cracking device needs to be developed. SUMMARY

[0004] In order to solve the problems in the prior art, the present application provides a carbon three and carbon four mixed fraction full hydrogenation catalyst, which is used for full hydrogenation of the carbon three and carbon four mixed fractions generated by the light raw material cracking, and the olefins and dienes are hydrogenated to saturated and then transported to a cracking furnace or used as other raw materials.

[0005] One of the purposes of the present application is to provide a carbon three and carbon four full hydrogenation catalyst, which comprises an alumina carrier and a main active component and an auxiliary active component supported on the alumina carrier, the surface of the alumina carrier contains at least one oxygen-containing group of a hydroxyl group, a carboxyl group and a lactone group, the main active component is Pd, and the auxiliary active component is at least one of Ag, As, Sn, Cr, In and a rare earth element. The auxiliary active component can be a commonly used metal auxiliary active component in the field, and in addition to the above listed metal elements, other commonly used active metal elements such as alkali metals and alkaline earth metals can also be used.

[0006] According to the present application, the carbon three and carbon four full hydrogenation catalyst:

[0007] The content of the hydroxyl group in the alumina carrier is 3-60 mmol / g, preferably 20-60 mmol / g; the content of the carboxyl group is 3-50 mmol / g, preferably 15-50 mmol / g; and the content of the lactone group is 3-40 mmol / g, preferably 3-30 mmol / g.

[0008] The specific surface area of the alumina carrier is 10-150 m 2 / g, the water absorption is 50-200%, the carrier strength is 30-200 N / pellet, the bulk density is 0.4-0.8 g / ml, the pore volume is 0.6-1.5 ml / g, and the particle size is 2-4 mm.

[0009] According to the present application, the alumina carrier contains abundant oxygen-containing groups, and preferably, the density of the oxygen-containing groups on the surface of the carrier is 0.15-5 mmol / m 2 , preferably 0.7-3 mmol / m 2 .

[0010] According to the present application, in the carbon three carbon four full hydrogenation catalyst:

[0011] The carrier can be pure alumina or a combination of alumina and other components, and the content of alumina is 50-98% based on the total weight of the alumina carrier;

[0012] The content of the main active component is 0.05-1% and the content of the auxiliary active component is 0.01-15% based on the weight of the alumina carrier; preferably, the content of the main active component is 0.05-0.5% and the content of the auxiliary active component is 0.01-10% based on the weight of the alumina carrier.

[0013] The second object of the present application is to provide a preparation method of the above-mentioned carbon three carbon four full hydrogenation catalyst, which comprises: loading a solution containing a metal compound of a main active component and a metal compound of an auxiliary active component onto an alumina carrier, drying and calcining to obtain the carbon three carbon four full hydrogenation catalyst.

[0014] According to the present application, in the preparation method of the carbon three carbon four full hydrogenation catalyst:

[0015] The metal compound of the main active component is selected from at least one of soluble compounds of palladium, preferably at least one of chloropalladium, palladium nitrate, palladium acetate and palladium sulfate;

[0016] The metal compound of the auxiliary active component is selected from at least one of chlorides, nitrates, acetates and sulfates of Ag, As, Sn, Cr, In and rare earth elements, and metal organic compounds;

[0017] the solvent in the solution is selected from at least one of water, hydrochloric acid, nitric acid, acetic acid, alcohol;

[0018] the drying condition is 60-160℃ for 4-24h, preferably 80-140℃ for 8-12h;

[0019] the calcination condition is 200-800℃ for 4-12h, preferably 300-700℃ for 6-10h.

[0020] The present application can employ any of the existing methods in the art to load the active component onto the carrier. According to the preferred embodiment of the present application, the loading method comprises employing a spraying method and / or an impregnation method to load the active component precursor onto the carrier.

[0021] According to the present application, the method for preparing the alumina carrier comprises kneading, granulating and surface treating raw materials including an aluminum source, a forming agent, a pore-expanding agent, an inorganic carbon species and a binder to obtain the alumina carrier.

[0022] According to the present application, the method for preparing the alumina carrier comprises:

[0023] the aluminum source is selected from at least one of boehmite, pseudoboehmite, alumina, aluminum hydroxide;

[0024] the forming agent is selected from at least one of polyethylene glycol cellulose, methyl cellulose, carboxymethyl cellulose, sodium hydroxymethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose, starch;

[0025] the pore-expanding agent is selected from at least one of sesbania gum, polyvinyl alcohol, polyethylene glycol, polyacrylamide, polypropylene glycol;

[0026] the inorganic carbon species is selected from at least one of coke, activated carbon, carbon black, white carbon black, glassy carbon, charcoal, bamboo charcoal, coconut shell charcoal, graphene, graphyne, diamond;

[0027] the binder is selected from at least one of inorganic acid, organic acid, preferably at least one of nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, acetic acid, ascorbic acid;

[0028] the inorganic carbon species is used in an amount of 1-40 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on the contained Al2O3;

[0029] the forming agent is used in an amount of 1-15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on the contained Al2O3;

[0030] The amount of the pore-expanding agent is 1-15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated as Al2O3.

[0031] According to the present application, in the preparation method of the alumina carrier,

[0032] The granulation process can adopt any existing molding technology in the art, such as at least one of fluidized granulation, agglomeration granulation, extrusion granulation, extrusion granulation or spray granulation.

[0033] The dried granulated material is subjected to surface treatment, and the drying process can adopt the drying equipment and drying conditions commonly used in the prior art, for example, the drying conditions are 40-140°C for 1-12h, preferably 60-120°C for 2-8h.

[0034] According to the present application, in the preparation method of the alumina carrier, the surface treatment is at least one of heat treatment, crystallization, oxidation, alkalization and irradiation treatment, wherein,

[0035] The heat treatment is carried out in an atmosphere comprising a first atmosphere and a second atmosphere, the first atmosphere is at least one of carbon dioxide, water vapor, acetylene, ethylene and methane, the second atmosphere is at least one of air, nitrogen, argon and helium, the volume ratio of the first atmosphere to the second atmosphere is (0.05-1):1, the temperature is 300-1200°C, the time is 1-24h, and the pressure is 0.1-3MPa.

[0036] The crystallization is carried out at a temperature of 120-250°C for 4-18h under a pressure of 0.2-15MPa, and the solvent used in the crystallization is at least one of water, ethanol, ethylene glycol and ethylenediamine;

[0037] The oxidation is carried out at a temperature of 30-80°C for 0.2-10h, and the oxidizing agent solution used in the oxidation is at least one of nitric acid, sulfuric acid, ammonium persulfate, hydrogen peroxide and potassium permanganate, and the concentration of the oxidizing agent solution is 0.1-10mol / L;

[0038] The alkalization is carried out at a temperature of 30-110°C for 0.2-10h, and the alkaline solution used in the alkalization is at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, sodium oxalate, sodium citrate, potassium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate and potassium citrate, and the concentration of the solution is 0.1-10mol / L;

[0039] The irradiation conditions are: the ray source is selected from gamma rays and / or microwaves, preferably, the gamma ray irradiation dose rate is 2-90 kGy / min, the time is 0.2-24 h; the power of the microwave is 50-1000 W, the time is 0.5-60 min.

[0040] In the present application, the alumina carrier and its preparation can refer to patent ZL202311028071.8, the relevant contents disclosed in the foregoing document are incorporated into the present application by reference. In the preparation process of the alumina-containing carrier, means such as heat treatment, crystallization, oxidation, irradiation treatment, and introduction of carbon species are adopted to change its crystal structure, surface isoelectric point, and local Al-O charge density to improve the types and quantities of oxygen-containing groups of the carrier.

[0041] The third object of the present application is to provide the use of the above-mentioned carbon three and carbon four full hydrogenation catalyst or the carbon three and carbon four full hydrogenation catalyst obtained by the above-mentioned preparation method in carbon three and carbon four mixed fraction full hydrogenation reaction. The "carbon three and carbon four mixed fraction full hydrogenation" refers to the hydrogenation of unsaturated hydrocarbons in the carbon three and carbon four mixture produced by the cracking device to saturation and then transported to the cracking furnace or used as other raw materials.

[0042] The present application provides a full hydrogenation catalyst for carbon three and carbon four mixed fraction produced by cracking of light weight raw materials, which comprises a main active component, an auxiliary active component, and a carrier. The main active component is Pd, the metal compound of the auxiliary active component is selected from at least one of Ag, As, Sn, Cr, In, and rare earth elements, and the carrier contains abundant oxygen-containing groups. In the preparation process of the carrier, means such as heat treatment, crystallization, oxidation, irradiation treatment, and introduction of carbon species are adopted to change its crystal structure, surface isoelectric point, and local Al-O charge density to improve the types and quantities of oxygen-containing groups of the carrier. By adopting the alumina carrier with adjustable surface oxygen-containing groups, the present application can effectively improve the dispersion of noble metals of the catalyst, expose more active sites, and improve the catalytic performance. DETAILED DESCRIPTION

[0043] The present application will be specifically described below in combination with specific examples. It is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments of the present application made by those skilled in the art according to the content of the present application still belong to the protection scope of the present application.

[0044] The raw materials used in the examples and comparative examples, if not particularly limited, are disclosed in the prior art, for example, can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0045] Example 1

[0046] 1. Preparation of alumina support

[0047] Take 100 g of pseudo-boehmite (specific surface area 206.5 m 2 / g, pore volume 0.93 ml / g, bulk density 0.24 g / ml), 20 g of γ-Al2O3 powder, 4.6 g of hydroxyethyl cellulose, 5.2 g of polyethylene glycol, 12 g of activated carbon, and put them into a kneader to mix uniformly. Take 6.9 g of ascorbic acid, 1.4 g of concentrated sulfuric acid, and add them into 120 ml of a solvent of ethanol and deionized water (volume ratio 5:1) to prepare a mixed solution. Add the prepared solution into the kneader, extrude and shape after kneading, and cut into particles to obtain cylindrical particles with a particle size of 2-4 mm. Dry the particles at 100°C for 4 h, crystallize at 200°C for 10 h, and then heat treat at 1180°C and 0.2 MPa with air and water vapor for 4 h, and then immerse in 2.0 mol / L hydrogen peroxide solution for 1 h and dry at 130°C for 6 h to obtain an alumina support S1.

[0048] 2. Preparation of full hydrogenation catalyst

[0049] Take 0.03 g of silver nitrate and 0.06 g of cerium nitrate and add them into 2 mL of palladium nitrate solution (Pd content 25 mg / mL), dilute with deionized water to 13.9 mL, and spray onto 20 g of alumina support S1. Put the sprayed sample into an oven to dry at 120°C for 6 h and then calcine at 400°C for 8 h to obtain a catalyst C1 with a Pd loading of 0.25 wt%, an Ag loading of 0.10 wt%, and a Ce loading of 0.10 wt%.

[0050] Example 2

[0051] 1. Preparation of alumina support

[0052] Take 120 g of pseudo-boehmite and 20 g of alumina trihydrate powder in Example 1, 4 g of starch, 6 g of polyvinyl alcohol, and 14 g of porous carbon, and put them into a kneader to mix uniformly. Take 2.2 g of concentrated nitric acid and add it into 125 g of deionized water, mix uniformly to prepare a mixed solution. Add the prepared solution into the kneader, extrude and shape after kneading, and cut into particles to obtain cylindrical particles with a particle size of 2-4 mm. Dry the particles at 80°C for 8 h, heat treat at 700°C and 1 MPa with carbon dioxide and nitrogen for 5 h, immerse in 4 mol / L potassium carbonate solution for 3 h, and irradiate with γ-rays at 5 kGy / min for 40 min to obtain an alumina support S2.

[0053] 2. Preparation of full hydrogenation catalyst

[0054] Take 0.16 g of cerium nitrate and add it to 2 mL of palladium nitrate solution (Pd content is 25 mg / mL), dilute to 15.2 mL with deionized water, and spray it onto 20 g of alumina carrier S2. After drying the sprayed sample in an oven at 120°C for 6 h and calcining it at 400°C for 8 h, catalyst C2 is obtained, with a Pd loading of 0.25 wt%, and a Ce loading of 0.25 wt%.

[0055] Example 3

[0056] 1. Preparation of the alumina carrier

[0057] Take 120 g of pseudoboehmite in Example 1, 20 g of γ-Al2O3 powder, 6 g of polyethylene glycol, 7 g of methyl cellulose, and 9 g of graphene, and mix them uniformly in a kneader. Then take 2 g of oxalic acid and 1.8 g of acetic acid, add them to 115 g of deionized water to prepare a mixed solution. Add the prepared solution to the kneader, and after kneading, extrude and cut it into 2-4 mm diameter cylindrical particles. After drying the particles at 80°C for 8 h, treat them with 800°C, 2 MPa carbon dioxide and air for 6 h, soak them in 1 mol / L potassium hydroxide solution for 1 h, and finally irradiate them with 400 w microwaves for 15 min to obtain the alumina carrier S3.

[0058] 2. Preparation of the full hydrogenation catalyst

[0059] Take 0.05 g of silver nitrate and 0.05 g of indium nitrate and add them to 2 mL of palladium nitrate solution (Pd content is 25 mg / mL), dilute to 10.5 mL with deionized water, and spray it onto 20 g of alumina carrier S3. After drying the sprayed sample in an oven at 120°C for 6 h and calcining it at 450°C for 8 h, catalyst C3 is obtained, with a Pd loading of 0.25 wt%, an Ag loading of 0.15 wt%, and an In loading of 0.10 wt%.

[0060] Example 4

[0061] 1. Preparation of the alumina carrier

[0062] The alumina carrier is the same as in Example 1.

[0063] 2. Preparation of the full hydrogenation catalyst

[0064] Take 0.06 g of lanthanum nitrate and add it to 2.4 mL of palladium nitrate solution (Pd content is 25 mg / mL), dilute to 13.9 mL with deionized water, and spray it onto 20 g of alumina carrier S1. After drying the sprayed sample in an oven at 120°C for 6 h and calcining it at 450°C for 8 h, catalyst C4 is obtained, with a Pd loading of 0.30 wt%, and a La loading of 0.10 wt%.

[0065] Example 5

[0066] 1. Preparation of alumina support

[0067] The preparation of alumina support was carried out according to the preparation procedure of Example 1, except that after drying, the sample was crystallized at 160°C for 10h, then soaked in 2.0mol / L ascorbic acid solution for 10h, and dried to obtain the alumina support S4.

[0068] 2. Preparation of full hydrogenation catalyst

[0069] The catalyst was prepared according to the method of Example 1, using the alumina support S4 as catalyst carrier, to obtain the catalyst C5, which has a Pd loading of 0.25wt%, Ag loading of 0.10wt%, and Ce loading of 0.10wt%.

[0070] Comparative Example 1

[0071] The alumina support was prepared according to the method of Example 1, except that the obtained cylindrical particles were dried and then calcined at 1180°C for 6h to obtain the alumina support S5. The catalyst was prepared according to the method of Example 1, using the alumina support S5 as catalyst carrier to obtain the catalyst D1.

[0072] Comparative Example 2

[0073] The commercially available finished alumina with a specific surface area of 83.5m 2 / g, bulk density of 0.68g / ml, strength of 63.1N / particle, and water absorption of 48.3% was used as the support S6. The catalyst was prepared according to the method of Example 1, using the alumina support S6 as catalyst carrier to obtain the catalyst D2.

[0074] Comparative Example 3

[0075] 2.4mL of palladium nitrate solution (Pd content of 25mg / mL) was weighed out and diluted to 9.6mL with deionized water, and sprayed onto 20g of the alumina support S6. The sprayed sample was dried in an oven at 120°C for 6h and then calcined at 400°C for 8h to obtain the catalyst D3, which has a Pd loading of 0.30wt%.

[0076] Comparative Example 4

[0077] The commercially available alumina support S6 was immersed in 2.0mol / L hydrogen peroxide solution for 1h and dried at 80°C for 5h to obtain the alumina support S7. The catalyst was prepared according to the method of Example 1, using the alumina support S7 as catalyst carrier to obtain the catalyst D4.

[0078] Test Example 1 Characterization of alumina-containing support

[0079] The specific surface area was measured by nitrogen physical adsorption BET method;

[0080] The bulk density was calculated by measuring the mass of 100 mL of the alumina carrier, and the average value was obtained after measuring each sample 3 times;

[0081] The strength was measured by a general particle strength measuring instrument, and the average value was obtained from 20 carrier measurement results;

[0082] The water absorption was obtained by measuring the weight gain after 20 g of the alumina carrier was soaked in water for 10 minutes, and the surface water was drained off;

[0083] The properties and quantity of the oxygen-containing groups of the carrier were determined by the Boehm chemical method.

[0084] Table 1. Physical property test results of the alumina carrier of the examples and the comparative examples

[0085]

[0086] The carrier oxygen-containing group analysis of the examples and the comparative examples was determined as follows: three 0.6 g carriers were weighed and soaked in 40 ml of 0.05 mol / L NaHCO3, Na2CO3 and NaOH solution respectively for 24 h. 10 ml of the soaked solution was titrated with 0.05 mol / L hydrochloric acid. Each sample was titrated three times, and the arithmetic average value was obtained. The quantity of each type of oxygen-containing group of the carrier was calculated according to the alkali consumption, and the oxygen-containing group density was obtained in combination with the specific surface area data of the carrier. The results are shown in Table 2.

[0087] Table 2. Test results of the oxygen-containing groups in the alumina carrier of the examples and the comparative examples

[0088]

[0089] As can be seen from Table 2, the content and density of the oxygen-containing groups on the surface of the alumina carrier prepared by the method of the present application are obviously higher. Meanwhile, by adjusting the raw material ratio, the preparation process parameters and conditions, the method of the present application can realize the regulation of the quantity and distribution of the oxygen-containing groups on the surface of the alumina carrier.

[0090] Test Example 2 Catalyst catalytic performance evaluation

[0091] 20 ml of the catalyst in the above examples 1-5 and comparative examples 1-4 was added into an adiabatic fixed bed reactor, and a carbon three carbon four mixed raw material was fed into the selective hydrogenation reactor from top to bottom. The reactor inlet temperature was 40℃, the pressure was 3.0 MPa, and the liquid hourly space velocity (LHSV) calculated based on the raw material feed rate was 40 h -1 , and the evaluation was carried out under the following conditions. The composition of the raw material is shown in Table 3, and the evaluation results are shown in Table 4.

[0092] Among them, the composition content of the raw material and the material after hydrogenation by each catalyst was detected by gas chromatography.

[0093] Unsaturated hydrocarbon conversion rate = (molar content of unsaturated hydrocarbon in raw material - molar content of unsaturated hydrocarbon in product) / molar content of unsaturated hydrocarbon in raw material * 100%

[0094] Table 3. Raw material composition

[0095]

[0096] Table 4. Catalyst evaluation results

[0097]

[0098] The content of components in the hydrogenated product in Table 4 is the weight percentage content after normalization calculation excluding the hydrogen content. The results of using the above catalyst for full hydrogenation of the carbon three carbon four mixed fraction show that the diene in the mixed fraction can be completely reacted using the catalyst in the present application, and the unsaturated hydrocarbon conversion rate is higher.

Claims

1. A C3-C4 full-range hydrogenation catalyst comprising: An alumina carrier, and a main active component and an auxiliary active component supported on the alumina carrier, the alumina carrier surface comprising oxygen-containing groups of at least one of hydroxyl, carboxyl, lactone, the main active component being Pd, and the auxiliary active component being at least one of Ag, As, Sn, Cr, In, and rare earth elements; the carrier being prepared by surface treatment and introduction of inorganic carbon species to improve the types of oxygen-containing groups, the surface treatment being at least one of heat treatment, crystallization, oxidation, alkalization, and irradiation treatment, and the inorganic carbon species being at least one of coke, activated carbon, carbon black, white carbon black, glassy carbon, charcoal, bamboo charcoal, coconut shell charcoal, graphene, graphyne, and diamond.

2. The carbon trim and carbon tetra full hydrogenation catalyst according to claim 1, characterized in that, The content of the hydroxyl groups in the alumina carrier is 3-60 mmol / g; and / or, The content of the carboxyl groups in the alumina carrier is 3-50 mmol / g; and / or, The content of the lactone groups in the alumina carrier is 3-40 mmol / g. The content of the hydroxyl groups in the alumina carrier is 20-60 mmol / g; and / or, 3. The carbon trimmer carbon tetramer full hydrogenation catalyst according to claim 2, characterized by, The content of the carboxyl groups in the alumina carrier is 15-50 mmol / g; and / or, The content of the lactone groups in the alumina carrier is 3-30 mmol / g.

4. The carbon three and carbon four full hydrogenation catalyst according to claim 1, wherein 5. The carbon three and carbon four full hydrogenation catalyst according to claim 1, wherein The content of alumina in the carrier is 50-98% based on the total weight of the alumina carrier; and / or The specific surface area of the alumina carrier is 10 ~ 150 m 2 / g, the water absorption is 50 ~ 200 %, the carrier strength is 30 ~ 200 N / pea, the bulk density is 0.4 ~ 0.8 g / ml, the pore volume is 0.6 ~ 1.5 ml / g, and the particle size is 2 ~ 4 mm. The content of the main active component is 0.05-1%, and the content of the auxiliary active component is 0.01-15% based on the weight of the alumina carrier.

6. The carbon three and carbon four full hydrogenation catalyst according to claim 5, wherein The content of the main active component is 0.05-0.5%, and the content of the auxiliary active component is 0.01-10% based on the weight of the alumina carrier. The solution containing the metal compound of the main active component and the metal compound of the auxiliary active component is supported on the alumina carrier, and after drying and calcination, the carbon three and carbon four full hydrogenation catalyst is obtained.

8. The preparation method according to claim 7, wherein 7. A process for preparing the carbon trim and carbon tetramer full hydrogenation catalyst according to any one of claims 1 to 6, comprising: The metal compound of the main active component is at least one of soluble compounds of palladium; and / or The metal compound of the auxiliary active component is at least one of chlorides, nitrates, acetates, sulfates, and metal organic compounds of Ag, As, Sn, Cr, In, and rare earth elements; and / or The solvent in the solution is at least one of water, hydrochloric acid, nitric acid, acetic acid, and alcohols; and / or The drying condition is 60-160°C for 4-24h; and / or The calcination condition is 200-800°C for 4-12h.

9. The preparation method according to claim 8, wherein The metal compound of the main active component is at least one of palladium chloride, palladium nitrate, palladium acetate, and palladium sulfate; and / or The drying condition is 80-140°C for 8-12h; and / or ​ ​ The calcination condition is 300-700℃ for 6-10h.

10. The preparation method according to claim 7, characterized in that, The preparation method of the alumina carrier comprises: kneading, granulating and surface treating raw materials including an aluminum source, a forming agent, a pore-expanding agent, an inorganic carbon species and a binder to obtain the alumina carrier.

11. The method of claim 10, wherein, In the preparation method of the alumina carrier, The aluminum source is at least one of boehmite, pseudoboehmite, alumina and aluminum hydroxide; and / or, The forming agent is at least one of polyethylene glycol cellulose, methyl cellulose, carboxymethyl cellulose, sodium hydroxymethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose and starch; and / or, The pore-expanding agent is at least one of sesbania gum, polyvinyl alcohol, polyethylene glycol, polyacrylamide and polypropylene glycol; and / or, The inorganic carbon species is at least one of coke, activated carbon, carbon black, white carbon black, glassy carbon, charcoal, bamboo charcoal, coconut shell charcoal, graphene, graphyne and diamond; and / or, The binder is at least one of inorganic acid and organic acid; and / or, The inorganic carbon species is used in an amount of 1-40 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on Al2O3 contained therein; and / or, The forming agent is used in an amount of 1-15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on Al2O3 contained therein; and / or, The pore-expanding agent is used in an amount of 1-15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on Al2O3 contained therein.

12. The method of claim 11, wherein, In the preparation method of the alumina carrier, The binder is at least one of nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, acetic acid and ascorbic acid.

13. The preparation method according to claim 10, characterized in that, The heat treatment condition is that: the atmosphere of the heat treatment comprises a first atmosphere and a second atmosphere, the first atmosphere is at least one of carbon dioxide, water vapor, acetylene, ethylene and methane, the second atmosphere is at least one of air, nitrogen, argon and helium, the volume ratio of the first atmosphere to the second atmosphere is (0.05-1):1, the temperature of the heat treatment is 300-1200℃, the time of the heat treatment is 1-24h, and the pressure is 0.1-3MPa; and / or, The crystallization condition is that: the temperature is 120-250℃, the time is 4-18h, the pressure is 0.2-15MPa, and the solvent used for the crystallization is at least one of water, ethanol, ethylene glycol and ethylenediamine; and / or, The oxidation condition is that: the temperature is 30-80℃, the time is 0.2-10h, the oxidant solution used for the oxidation is a solution of at least one of nitric acid, sulfuric acid, ammonium persulfate, hydrogen peroxide and potassium permanganate, and the concentration of the oxidant solution is 0.1-10mol / L; and / or, The alkalization conditions are: temperature 30-110°C, time 0.2-10h, the alkaline solution used for alkalization is selected from at least one of the following: sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, sodium oxalate, sodium citrate, potassium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate, potassium citrate, the solution concentration is 0.1-10 mol / L; and / or, The irradiation conditions are: the ray source is selected from γ ray and / or microwave.

14. The preparation method according to claim 13, characterized in that, The γ ray irradiation dose rate is 2-90 kGy / min, time is 0.2-24h; and / or, the microwave power is 50-1000W, time is 0.5-60min.

15. The carbon three carbon four full hydrogenation catalyst according to any one of claims 1-6 or obtained by the preparation method according to any one of claims 7-14, in the application in carbon three carbon four fraction hydrogenation reaction.

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