C3 and C4 full hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention provides a C3 and C4 total hydrogenation catalyst as well as a preparation method and application thereof. According to the C3 and C4 total hydrogenation catalyst, unsaturated hydrocarbon in C3 and C4 fractions generated by a lightweight raw material cracking device can be completely hydrogenated to be saturated. The catalyst comprises a main active component, an auxiliary active component and a carrier. According to the invention, the distribution of metal active components is controlled and the conversion rate of unsaturated hydrocarbon is improved by regulating and controlling the type, number and density of oxygen-containing groups of the carrier.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and specifically relates to a C3C4 full hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Petrochemical industry is an important industry related to the national economy and people's livelihood, and ethylene plant is a production plant for a variety of organic chemical raw materials. At present, the raw materials used by ethylene plants at home and abroad are mainly naphtha, ethane, propane, butane, diesel, coal, etc. Compared with traditional naphtha cracking, light raw materials can increase ethylene yield, reduce energy consumption, and improve the economic benefits of enterprises. In addition to the main product ethylene, cracking plants using light raw materials produce by-products such as hydrogen, methane, carbon three, carbon four, as well as benzene and toluene. Among them, the content of unsaturated carbon three and carbon four is relatively small, mainly including propylene, propyne (MA), propadiene (PD), butadiene and butene. The cost of selecting hydrogenation after separation is relatively high, and they are usually fully hydrogenated and transported to the cracking furnace for use as cracking raw materials.

[0003] The existing technical solutions mainly focus on hydrogenating the C3 or C4 fractions separately, or loading the C3 and C4 hydrogenation catalysts in layers in the hydrogenation reactor of the mixed stream. Therefore, it is necessary to develop a full hydrogenation catalyst suitable for the mixed C3 and C4 fractions produced by the light feed cracking unit. Summary of the invention

[0004] In order to solve the problems existing in the prior art, the present invention proposes a C3C4 mixed fraction full hydrogenation catalyst, which is used for the full hydrogenation of the C3C4 mixed fraction produced by cracking light raw materials, and the olefins and diolefins are hydrogenated to saturation and then transported to the cracking furnace or used as other raw materials.

[0005] One of the purposes of the present invention is to provide a C3C4 full hydrogenation catalyst, comprising: an alumina carrier, and a main active component and a co-active component supported on the alumina carrier, wherein the surface of the alumina carrier contains at least one oxygen-containing group of hydroxyl, carboxyl, and lactone, the main active component is Pd, and the co-active component is at least one of Ag, As, Sn, Cr, In, and rare earth elements. The co-active component can be a metal co-active component commonly used in the art, and in addition to the metal elements listed above, other commonly used active metal elements, such as alkali metals, alkaline earth metals, etc., can also be used.

[0006] According to the present invention, the C3C4 full hydrogenation catalyst is:

[0007] In the alumina carrier, the content of the hydroxyl group is 3 to 60 mmol / g, preferably 20 to 60 mmol / g; the content of the carboxyl group is 3 to 50 mmol / g, preferably 15 to 50 mmol / g; the content of the lactone group is 3 to 40 mmol / g, preferably 3 to 30 mmol / g;

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

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

[0010] According to the present invention, in the C3C4 full hydrogenation catalyst:

[0011] The carrier may 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 as 100%;

[0012] Based on the weight of the alumina carrier as 100%, the main active component is 0.05-1%, and the auxiliary active component is 0.01-15%; preferably, based on the weight of the alumina carrier as 100%, the main active component is 0.05-0.5%, and the auxiliary active component is 0.01-10%.

[0013] The second object of the present invention is to provide a method for preparing the above-mentioned C3C4 full hydrogenation catalyst, comprising: loading a solution of a metal compound containing a main active component and a metal compound of an auxiliary active component onto an alumina carrier, and after drying and calcining, obtaining the C3C4 full hydrogenation catalyst.

[0014] According to the present invention, in the method for preparing the C3C4 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 palladium chloride, palladium nitrate, palladium acetate and palladium sulfate;

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

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

[0018] The drying conditions are: drying at 60-160°C for 4-24 hours, preferably, drying at 80-140°C for 8-12 hours;

[0019] The calcination conditions are: calcination at 200-800° C. for 4-12 h, preferably, calcination at 300-700° C. for 6-10 h.

[0020] The present invention can adopt any existing method for preparing supported catalysts in the art to load the active component onto the carrier. According to a preferred embodiment of the present invention, the loading method includes loading the active component precursor onto the carrier by spraying and / or impregnation.

[0021] According to the present invention, the preparation method of the alumina carrier comprises: kneading, granulating and surface treating raw materials including an aluminum source, a molding agent, a pore-enlarging agent, an inorganic carbon species and a binder to obtain the alumina carrier.

[0022] According to the present invention, in the method for preparing the alumina carrier:

[0023] The aluminum source is selected from at least one of boehmite, pseudo-boehmite, alumina, and aluminum hydroxide;

[0024] The molding 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 and starch;

[0025] The pore-enlarging agent is selected from at least one of sesbania powder, polyvinyl alcohol, polyethylene glycol, polyacrylamide, and polypropylene glycol;

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

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

[0028] In parts by mass, the amount of the inorganic carbon species is 1 to 40 parts relative to 100 parts of the aluminum source, wherein the aluminum source is based on the Al content. 2 O 3 Come to plan;

[0029] In parts by mass, the amount of the forming agent is 1 to 15 parts relative to 100 parts of the aluminum source, wherein the aluminum source is based on the content of Al2 O 3 Come to plan;

[0030] In parts by mass, the amount of the pore expanding agent is 1 to 15 parts relative to 100 parts of the aluminum source, wherein the aluminum source is based on the content of Al 2 O 3 Come to plan.

[0031] According to the present invention, in the method for preparing the alumina carrier:

[0032] The granulation process may adopt any existing forming technology in the art, such as at least one of fluidized granulation, agglomeration granulation, extrusion granulation, compression granulation or spray granulation;

[0033] The granulated material is dried before surface treatment. The drying process may adopt the drying equipment and drying conditions commonly used in the prior art. For example, the drying process may be carried out at 40 to 140° C. for 1 to 12 hours, preferably at 60 to 120° C. for 2 to 8 hours.

[0034] According to the present invention, in the method for preparing the alumina carrier, the surface treatment is selected from at least one of heat treatment, crystallization, oxidation, alkalization, and irradiation treatment, wherein:

[0035] The heat treatment conditions are as follows: the heat treatment atmosphere includes a first atmosphere and a second atmosphere, the first atmosphere is selected from at least one of carbon dioxide, water vapor, acetylene, ethylene, and methane, the second atmosphere is selected from 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 heat treatment temperature is 300-1200°C, the heat treatment time is 1-24h, and the pressure is 0.1-3MPa;

[0036] The crystallization conditions are: temperature of 120-250°C, time of 4-18h, pressure of 0.2-15MPa, and the solvent used for crystallization is selected from at least one of water, ethanol, ethylene glycol, and ethylenediamine;

[0037] The oxidation conditions are: temperature of 30-80°C, time of 0.2-10h, the oxidant solution used for oxidation is selected from at least one of nitric acid, sulfuric acid, ammonium persulfate, hydrogen peroxide, potassium permanganate, and ascorbic acid, and the concentration of the oxidant solution is 0.1-10 mol / L;

[0038] The alkalization conditions are as follows: the temperature is 30-110° C., the time is 0.2-10 h, the alkaline solution used for alkalization is selected from 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 solution concentration is 0.1-10 mol / L;

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

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

[0041] The third object of the present invention is to provide the above-mentioned C3C4 full hydrogenation catalyst or the C3C4 full hydrogenation catalyst obtained by the above-mentioned preparation method, and its application in the full hydrogenation reaction of C3C4 mixed fraction. The "full hydrogenation of C3C4 mixed fraction" refers to hydrogenating the unsaturated hydrocarbons in the C3 and C4 mixture produced by the cracking unit to saturation and then transporting them to the cracking furnace or using them as other raw materials.

[0042] The present invention provides a full hydrogenation catalyst for a C3C4 mixed fraction produced by cracking light raw materials, the catalyst comprising a main active component, a co-active component and a carrier. The main active component is Pd, the metal compound of the co-active component is selected from at least one of Ag, As, Sn, Cr, In and rare earth elements, and the carrier contains rich oxygen-containing groups. In the preparation process of the carrier, heat treatment, crystallization, oxidation, irradiation treatment, introduction of carbon species and other means are adopted to change its crystal structure, surface isoelectric point and local Al-O charge density to increase the types and quantity of oxygen-containing groups on the carrier. The present invention uses alumina with adjustable surface oxygen-containing groups as a carrier, which can effectively improve the precious metal dispersion of the catalyst, expose more active sites and improve the catalytic performance. DETAILED DESCRIPTION

[0043] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0044] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0045] Example 1

[0046] 1. Preparation of alumina carrier

[0047] Weigh 100 g of pseudo-boehmite (specific surface area 206.5 m 2 / g, pore volume 0.93ml / g, bulk density 0.24g / ml), 20gγ-Al 2 O 3 Powder, 4.6g hydroxyethyl cellulose, 5.2g polyethylene glycol, 12g activated carbon, put into a kneader and mix evenly. Weigh 6.9g ascorbic acid, 1.4g concentrated sulfuric acid, add 120ml ethanol and deionized water (volume ratio 5:1) solvent to prepare a mixed solution. Add the prepared solution into the kneader, knead and extrude into pellets to obtain cylindrical particles with a particle size of 2-4mm. Dry the particles at 100℃ for 4h, crystallize at 200℃ for 10h, then heat treat with air and water vapor at 1180℃ and 0.2MPa for 4h, then immerse in 2.0mol / L hydrogen peroxide for 1h, and dry at 130℃ for 6h to obtain alumina carrier S1.

[0048] 2. Preparation of full hydrogenation catalyst

[0049] 0.03 g of silver nitrate and 0.06 g of cerium nitrate were weighed and added to 2 mL of palladium nitrate solution (Pd content was 25 mg / mL), diluted to 13.9 mL with deionized water, and sprayed onto 20 g of alumina support S1. The sprayed sample was placed in an oven and dried at 120° C. for 6 h, and then calcined at 400° C. for 8 h to obtain catalyst C1, whose Pd loading was 0.25 wt%, Ag loading was 0.10 wt%, and Ce loading was 0.10 wt%.

[0050] Example 2

[0051] 1. Preparation of alumina carrier

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

[0053] 2. Preparation of full hydrogenation catalyst

[0054] 0.16 g of cerium nitrate was weighed and added to 2 mL of palladium nitrate solution (Pd content was 25 mg / mL), diluted to 15.2 mL with deionized water, and sprayed onto 20 g of alumina carrier S2. The sprayed sample was placed in an oven and dried at 120° C. for 6 h, and then calcined at 400° C. for 8 h to obtain catalyst C2, whose Pd loading was 0.25 wt % and Ce loading was 0.25 wt %.

[0055] Example 3

[0056] 1. Preparation of alumina carrier

[0057] Weigh 120 g of pseudo-boehmite and 20 g of γ-Al 2 O 3 Powder, 6g polyethylene glycol, 7g methyl cellulose, 9g graphene, put into a kneader and mix evenly. Then weigh 2g oxalic acid and 1.8g acetic acid, add to 115g deionized water, and prepare a mixed solution. Add the prepared solution into the kneader, knead and extrude into pellets to obtain cylindrical particles with a particle size of 2-4mm. After drying the particles at 80℃ for 8h, heat treat them with 800℃, 2MPa carbon dioxide and air for 6h, soak them in 1mol / L potassium hydroxide solution for 1h, and finally irradiate them with 400w microwave for 15min to obtain alumina carrier S3.

[0058] 2. Preparation of full hydrogenation catalyst

[0059] 0.05 g of silver nitrate and 0.05 g of indium nitrate were weighed and added to 2 mL of palladium nitrate solution (Pd content was 25 mg / mL), diluted to 10.5 mL with deionized water, and sprayed onto 20 g of alumina carrier S3. The sprayed sample was placed in an oven and dried at 120° C. for 6 h and then calcined at 450° C. for 8 h to obtain catalyst C3, whose Pd loading was 0.25 wt%, Ag loading was 0.15 wt%, and In loading was 0.10 wt%.

[0060] Example 4

[0061] 1. Preparation of alumina carrier

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

[0063] 2. Preparation of full hydrogenation catalyst

[0064] 0.06 g of lanthanum nitrate was weighed and added to 2.4 mL of palladium nitrate solution (Pd content was 25 mg / mL), diluted to 13.9 mL with deionized water, and sprayed onto 20 g of alumina support S1. The sprayed sample was placed in an oven and dried at 120° C. for 6 h, and then calcined at 450° C. for 8 h to obtain catalyst C4, whose Pd loading was 0.30 wt % and La loading was 0.10 wt %.

[0065] Example 5

[0066] 1. Preparation of alumina carrier

[0067] The alumina carrier was prepared by the preparation process of Example 1, except that after drying, it was crystallized at 160° C. for 10 h, then immersed in a 2.0 mol / L ascorbic acid solution for 10 h, and dried to obtain the alumina carrier S4.

[0068] 2. Preparation of full hydrogenation catalyst

[0069] The method of Example 1 was adopted to prepare a catalyst using alumina carrier S4 as a catalyst carrier to obtain catalyst C5, which had a Pd loading of 0.25 wt%, an Ag loading of 0.10 wt%, and a Ce loading of 0.10 wt%.

[0070] Comparative Example 1

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

[0072] Comparative Example 2

[0073] Take the commercially available specific surface area of ​​83.5m 2 / g, bulk density of 0.68g / ml, strength of 63.1N / particle, and water absorption rate of 48.3% finished alumina was used as carrier S6. The catalyst preparation method was the same as in Example 1, and catalyst D2 was obtained by using alumina carrier S6 as the catalyst carrier.

[0074] Comparative Example 3

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

[0076] Comparative Example 4

[0077] Alumina carrier S7 was obtained by impregnating commercially available alumina carrier S6 in 2.0 mol / L hydrogen peroxide for 1 hour and drying at 80°C for 5 hours. The catalyst preparation method was the same as in Example 1, and catalyst D4 was obtained by using alumina carrier S7 as the catalyst carrier.

[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 alumina support, and the average value was taken after measuring each sample three times;

[0081] The strength was measured using a universal particle strength measuring instrument, and the average value of the measurement results of 20 carrier particles was taken;

[0082] The water absorption rate is obtained by taking 20g of alumina carrier, soaking it in water for 10 minutes, taking it out and draining the surface water, and measuring the weight increase;

[0083] The nature and quantity of oxygen-containing groups in the carrier were determined by Boehm chemistry.

[0084] Table 1. Physical property test results of alumina carriers of Examples and Comparative Examples

[0085]

[0086] Analysis of oxygen-containing groups in carriers of the examples and comparative examples: Weigh three portions of 0.6 g of the carrier and place them in 40 ml of 0.05 mol / L NaHCO 3 、Na 2 CO 3 and NaOH solution for 24 hours. 10 ml of the soaking solution was titrated with 0.05 mol / L hydrochloric acid. Each sample was titrated three times, and the arithmetic mean was taken. The number of various oxygen-containing groups on the carrier was calculated based on the consumption of alkali, and the oxygen-containing group density was obtained in combination with the carrier specific surface data. The results are listed in Table 2.

[0087] Table 2. Test results of oxygen-containing groups in alumina supports of Examples and Comparative Examples

[0088]

[0089] It can be seen from Table 2 that the content and density of oxygen-containing groups on the surface of the alumina support prepared by the method of the present invention are significantly higher. At the same time, by adjusting the raw material ratio, preparation process parameters and conditions, the method of the present invention can achieve the regulation of the number and distribution of oxygen-containing groups on the surface of the alumina support.

[0090] Test Example 2 Catalytic Performance Evaluation of Catalyst

[0091] 20 ml of the catalysts in Examples 1 to 5 and Comparative Examples 1 to 4 were added to an adiabatic fixed bed reactor, and the C3-C4 mixed feedstock was fed into the selective hydrogenation reactor from top to bottom. The reactor inlet temperature was 40° C., the pressure was 3.0 MPa, and the liquid space velocity (LHSV) calculated based on the feed amount was 40 h -1 The composition of the raw materials is shown in Table 3, and the evaluation results are shown in Table 4.

[0092] Among them, gas chromatography is used to detect the component content of the raw material and the material after hydrogenation using various catalysts.

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

[0094] Table 3. Raw material composition

[0095]

[0096] Table 4 Catalyst evaluation results

[0097]

[0098] The contents of the components in the hydrogenated products in Table 4 are the weight percentages calculated after deducting the hydrogen content. The results of using the above catalyst for full hydrogenation of C3C4 mixed fractions show that the use of the catalyst of the present invention can completely react the dienes in the mixed fractions, and the conversion rate of unsaturated hydrocarbons is higher.

Claims

1. A C3C4 full hydrogenation catalyst comprising: An alumina carrier, and a main active component and an auxiliary active component supported on the alumina carrier, wherein the surface of the alumina carrier contains at least one oxygen-containing group selected from the group consisting of hydroxyl, carboxyl, and lactone, the main active component is Pd, and the auxiliary active component is at least one selected from the group consisting of Ag, As, Sn, Cr, In, and rare earth elements.

2. The C3C4 full hydrogenation catalyst according to claim 1, characterized in that In the alumina carrier: The content of the hydroxyl group is 3 to 60 mmol / g, preferably 20 to 60 mmol / g; and / or, The content of the carboxyl group is 3 to 50 mmol / g, preferably 15 to 50 mmol / g; and / or, The content of the lactone group is 3 to 40 mmol / g, preferably 3 to 30 mmol / g.

3. The C3C4 full hydrogenation catalyst according to claim 1, characterized in that The specific surface area of ​​the alumina carrier is 10 to 150 m 2 / g, water absorption rate is 50-200%, carrier strength is 30-200N / particle, bulk density is 0.4-0.8g / ml, pore volume is 0.6-1.5ml / g, and particle size is 2-4mm.

4. The C3C4 full hydrogenation catalyst according to claim 1, characterized in that Based on the total weight of the alumina carrier as 100%, the content of alumina in the carrier is 50-98%; and / or, Based on the weight of the alumina carrier as 100%, the main active component is 0.05-1%, and the auxiliary active component is 0.01-15%; preferably, based on the weight of the alumina carrier as 100%, the main active component is 0.05-0.5%, and the auxiliary active component is 0.01-10%.

5. A method for preparing the C3C4 full hydrogenation catalyst according to any one of claims 1 to 4, comprising: The solution containing the metal compound of the main active component and the metal compound of the auxiliary active component is loaded onto an alumina carrier, and after drying and calcining, the C3C4 full hydrogenation catalyst is obtained.

6. The preparation method according to claim 5, characterized in that: The metal compound of the main active component is selected from at least one of soluble compounds of palladium, preferably at least one of palladium chloride, palladium nitrate, palladium acetate and palladium sulfate; and / or, The metal compound of the auxiliary active component is selected from at least one of Ag, As, Sn, Cr, In, chlorides, nitrates, acetates, sulfates and metal organic compounds of rare earth elements; and / or, The solvent in the solution is selected from at least one of water, hydrochloric acid, nitric acid, acetic acid and alcohols; and / or, The drying conditions are: drying at 60-160°C for 4-24 hours, preferably, drying at 80-140°C for 8-12 hours; and / or, The calcination conditions are: calcination at 200-800° C. for 4-12 h, preferably, calcination at 300-700° C. for 6-10 h.

7. The preparation method according to claim 5, characterized in that: The preparation method of the alumina carrier comprises: kneading, granulating and surface treating raw materials including an aluminum source, a molding agent, a pore-enlarging agent, an inorganic carbon species and a binder to obtain the alumina carrier.

8. The preparation method according to claim 7, characterized in that: In the preparation method of the alumina carrier: The aluminum source is selected from at least one of boehmite, pseudo-boehmite, alumina, and aluminum hydroxide; and / or, The molding 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 and starch; and / or, The pore-enlarging agent is selected from at least one of sesbania powder, polyvinyl alcohol, polyethylene glycol, polyacrylamide and polypropylene glycol; and / or, The inorganic carbon species is selected from at least one of coke, activated carbon, carbon black, white carbon, glassy carbon, charcoal, bamboo charcoal, coconut shell charcoal, graphene, graphyne, and diamond; and / or, The binder is selected from at least one of inorganic acids and organic acids, preferably at least one of nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, acetic acid and ascorbic acid; and / or, The inorganic carbon species is used in an amount of 1 to 40 parts by mass relative to 100 parts by mass of the aluminum source, wherein the aluminum source is calculated based on the Al2O3 contained; and / or, The amount of the forming agent used is 1 to 15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on the Al2O3 contained; and / or, The amount of the pore expanding agent used is 1 to 15 parts by mass relative to 100 parts of the aluminum source, wherein the aluminum source is calculated based on the contained Al2O3.

9. The preparation method according to claim 7, characterized in that: In the method for preparing the alumina carrier, the surface treatment is selected from at least one of heat treatment, crystallization, oxidation, alkalization, and irradiation treatment.

10. The preparation method according to claim 9, characterized in that: The heat treatment conditions are as follows: the heat treatment atmosphere includes a first atmosphere and a second atmosphere, the first atmosphere is selected from at least one of carbon dioxide, water vapor, acetylene, ethylene, and methane, the second atmosphere is selected from 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 heat treatment temperature is 300-1200°C, the heat treatment time is 1-24h, and the pressure is 0.1-3MPa; and / or, The crystallization conditions are: temperature of 120-250° C., time of 4-18 hours, pressure of 0.2-15 MPa, and the solvent used for crystallization is selected from at least one of water, ethanol, ethylene glycol, and ethylenediamine; and / or, The oxidation conditions are: temperature of 30-80° C., time of 0.2-10 h, the oxidant solution used for oxidation is selected from at least one of nitric acid, sulfuric acid, ammonium persulfate, hydrogen peroxide, potassium permanganate, and ascorbic acid, and the concentration of the oxidant solution is 0.1-10 mol / L; and / or, The alkalization conditions are: temperature of 30-110° C., time of 0.2-10 h, the alkaline solution used for alkalization is selected from 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 solution concentration is 0.1-10 mol / L; and / or, 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; and / or the microwave power is 50-1000 W, the time is 0.5-60 min.

11. Use of the C3-C4 full hydrogenation catalyst as described in any one of claims 1 to 4 or the C3-C4 full hydrogenation catalyst obtained by the preparation method as described in any one of claims 5 to 10 in the hydrogenation reaction of a C3-C4 fraction.

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