阅读说明：本技术 基于复合氧化物载体的加氢催化剂及其制备方法与应用 (Hydrogenation catalyst based on composite oxide carrier and preparation method and application thereof ) 是由 杨晨熹 毛祖旺 乐毅 铁锴 彭晖 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种基于复合氧化物载体的加氢催化剂及其制备方法与应用,所述催化剂包括复合氧化物载体和负载于其上的活性组分,所述复合氧化物载体中含有0.01～3wt％的卤素元素,所述复合氧化物选自氧化铝和其它氧化物的组合,所述其它氧化物选自氧化硅、氧化钛、氧化钡和氧化钙中至少一种；所述活性组分包括第一活性组分、第二活性组分和第三活性组分,所述第一活性组分为钯,所述第二活性组分选自Ni、Ga、Ag、Bi、Cu、Zn、Ce、In中的至少一种,所述第三活性组分选自La、K、Na、Mo中的至少一种。所述加氢催化剂可以用于碳二加氢反应,在满足乙炔加氢脱除要求的同时乙烯的选择性高,乙烯的损失小,氢气消耗量少。(The invention discloses a hydrogenation catalyst based on a composite oxide carrier and a preparation method and application thereof, wherein the catalyst comprises the composite oxide carrier and an active component loaded on the composite oxide carrier, the composite oxide carrier contains 0.01-3 wt% of halogen elements, the composite oxide is selected from the combination of alumina and other oxides, and the other oxides are selected from at least one of silicon oxide, titanium oxide, barium oxide and calcium oxide; the active component comprises a first active component, a second active component and a third active component, wherein the first active component is palladium, the second active component is at least one selected from Ni, Ga, Ag, Bi, Cu, Zn, Ce and In, and the third active component is at least one selected from La, K, Na and Mo. The hydrogenation catalyst can be used for a carbon dioxide hydrogenation reaction, meets the requirement of acetylene hydrogenation removal, and simultaneously has high ethylene selectivity, small ethylene loss and low hydrogen consumption.)

1. A hydrogenation catalyst based on a composite oxide carrier, which comprises the composite oxide carrier and an active component loaded on the composite oxide carrier, wherein the composite oxide carrier contains 0.01-3 wt% of halogen elements, the composite oxide is selected from the combination of alumina and other oxides, and the other oxides are selected from at least one of silica, titania, barium oxide and calcium oxide; the active components include a first active component, a second active component, and a third active component.

2. The hydrogenation catalyst according to claim 1,

the halogen element is selected from fluorine element and/or chlorine element, preferably, the halogen element accounts for 0.01-2 wt% of the total mass of the composite oxide carrier, preferably 0.01-1 wt%; and/or

The specific surface area of the composite oxide carrier is 10-140 m²The water absorption is more than 30%, the bulk density is 0.3-1.0 g/mL, and the pore volume is 0.2-1.2 mL/g.

3. The hydrogenation catalyst according to claim 1, wherein the mass content of the active component is 0.01-20 wt% and the mass content of the composite oxide carrier is 80-99.9 wt%, based on 100 wt% of the mass of the catalyst; preferably, the mass content of the active component is 0.01-10 wt%, and the mass content of the composite oxide carrier is 90-99.9 wt%.

4. The hydrogenation catalyst according to any one of claims 1 to 3,

the first active component is palladium, and the mass content of the palladium is preferably 0.005-3 wt%, and preferably 0.025-1.5 wt%, based on 100 wt% of the mass of the catalyst; and/or

The second active component is selected from at least one of Ni, Ga, Ag, Bi, Cu, Zn, Ce and In, and preferably, the mass content of the second active component is 0.01-15 wt%, preferably 0.05-8 wt%, based on 100 wt% of the mass of the catalyst; and/or

The third active component is selected from at least one of La, K, Na and Mo, and preferably, the mass content of the third active component is 0.01-5 wt%, preferably 0.02-3 wt%, based on 100 wt% of the mass of the catalyst.

5. A method for preparing a hydrogenation catalyst based on a composite oxide carrier, preferably for preparing a hydrogenation catalyst according to any one of claims 1 to 4, comprising the steps of:

(1) mixing powder raw materials, wherein the powder raw materials comprise a composite oxide, a pore-expanding agent and a forming agent;

(2) adding organic matter containing halogen element and acidic aqueous solution;

(3) kneading, molding, granulating, drying and roasting to obtain a composite oxide carrier;

(4) and loading an active component on the composite oxide carrier, and drying and roasting to obtain the catalyst.

6. The production method according to claim 5,

the composite oxide is selected from the group consisting of alumina and other oxides selected from at least one of silica, titania, barium oxide and calcium oxide; preferably, the mass ratio of the other oxides to the alumina is (0.2-30): 100, preferably (0.5-15): 100; and/or

The pore-expanding agent is selected from at least one of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polypropylene glycol, sesbania powder, carbon black and white carbon black; preferably, the mass ratio of the pore-expanding agent to the composite oxide is (0.1-8): 100, preferably (0.2-6): 100; and/or

The forming agent is at least one selected from polyethylene glycol cellulose, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl methyl cellulose and starch; preferably, the weight ratio of the forming agent to the composite oxide is (0.1-5): 100, preferably (0.2-2): 100.

7. The method according to claim 5, wherein the organic material containing a halogen element is selected from an organic material containing a fluorine element and/or an organic material containing a chlorine element;

preferably, the fluorine-containing organic substance is at least one selected from the group consisting of trifluoroethanol, tetrafluoropropanol, trifluoroacetal hydrate, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, trifluoropropionic acid, fluoropropanol, difluoropropanol, trifluoropropanol, polytetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene-ethylene copolymer, and polyvinyl fluoride; and/or

Preferably, the organic matter containing chlorine element is at least one selected from chloroacetic acid, dichloroacetic acid, trichloroacetic acid, dichloropropionic acid, chloropropanol, trichloroethanol, poly tetrachloroethylene-ethylene copolymer, polyvinylidene chloride, polyvinyl chloride and trichloroacetic acid.

8. The production method according to claim 5, wherein the weight ratio of the organic material containing halogen elements to the composite oxide is (0.01-3): 100, preferably (0.01-2): 100, wherein the amount of the organic material containing halogen elements is based on the mass of the halogen elements.

9. The production method according to claim 5, wherein in the step (2), the acidic aqueous solution is an aqueous solution containing an organic acid and/or an inorganic acid;

preferably, the organic acid is selected from at least one of oxalic acid, formic acid, acetic acid, citric acid and tartaric acid, preferably from at least one of oxalic acid, citric acid and tartaric acid; the inorganic acid is at least one of nitric acid, sulfuric acid and hydrochloric acid;

more preferably, the concentration of the acidic aqueous solution is 0.005-0.5 mol/L, preferably 0.01-0.2 mol/L.

10. The production method according to any one of claims 5 to 9, characterized in that, in step (4), a solution containing an active component is sprayed on the composite oxide support; preferably, the active components include a first active component, a second active component, and a third active component; more preferably still, the first and second liquid crystal compositions are,

the first active component compound is at least one selected from palladium chloride, palladium nitrate and palladium acetate; preferably, the amount of the first active component compound is 0.005-3 wt%, preferably 0.025-1.5 wt%, based on 100 wt% of the catalyst, wherein the amount of the first active component compound is based on the content of the first active component; and/or

The second active component compound is selected from at least one of soluble nitrates, acetates and chlorides of Ni, Ga, Ag, Bi, Cu, Zn, Ce and In; preferably, the amount of the second active component-containing compound is 0.01-15 wt%, preferably 0.05-8 wt%, based on 100 wt% of the catalyst, wherein the amount of the second active component-containing compound is calculated by the content of the second active component therein; and/or

The third active component compound is selected from at least one of soluble nitrates, acetates and chlorides of La, K, Na and Mo; preferably, the amount of the compound containing the third active component is 0.01-5 wt%, preferably 0.02-3 wt% based on 100 wt% of the catalyst, wherein the amount of the compound containing the third active component is calculated by the content of the third active component.

11. The production method according to claim 10,

in step (3), the drying is performed as follows: drying at 60-160 ℃ for 3-48 h, preferably at 80-120 ℃ for 5-20 h; and/or

In step (3), the firing is performed as follows: roasting at 400-1500 ℃ for 3-48 h, preferably at 700-1200 ℃ for 5-30 h; and/or

In step (4), the drying is performed as follows: drying at 60-160 ℃ for 3-48 h, preferably at 80-120 ℃ for 5-20 h; and/or

In the step (4), the firing is performed as follows: roasting at 300-700 ℃ for 2-48 h, preferably 400-500 ℃ for 3-25 h.

12. A hydrogenation catalyst based on a composite oxide carrier obtained by the preparation method of any one of claims 5 to 11.

13. Use of a composite oxide support-based hydrogenation catalyst according to any one of claims 1 to 4 or claim 12 in acetylene removal reactions of ethylene feed gas.

Technical Field

The invention belongs to the field of catalysts, and particularly relates to a hydrogenation catalyst based on a composite oxide carrier and a preparation method thereof.

Background

In petrochemical production, a selective catalytic hydrogenation method is usually applied to a cracked gas C2 fraction to remove acetylene impurities in the cracked gas, so as to obtain a polymerization-grade ethylene raw material. The continuous rise of petroleum price leads to the rise of the price of downstream chemical products, and the requirement of the process on the purity of ethylene raw materials is also continuously increased, which puts higher requirements on the catalytic performance of the selective hydrogenation catalyst.

The selective hydrogenation catalyst for industrial use is usually a supported noble metal catalyst, which is mainly composed of a carrier and an active component. Modification of the support or control of the composition, structure and morphology of the active metal is the most common means for improving the performance of the catalyst.

Chinese patent CN103977794A discloses a supported three-dimensional structure noble metal catalyst and a preparation method thereof, wherein a one-step nucleation-self-assembly method is adopted, and a loose and porous supported three-dimensional structure noble metal catalyst with uniform size and appearance can be obtained by using a proper stabilizer and a proper reducing agent, and the acetylene catalytic selectivity is superior to that of a common catalyst.

Chinese patent CN101450308A discloses a carbon supported noble metal catalyst, which is improved in reactivity, selectivity and stability after acid treatment and oxidation treatment of a carrier.

Chinese patent CN102553579A introduces a preparation method of a high-dispersion supported nano metal catalyst, and stirring, ultrasound, roasting, alkali-free solution reduction and vacuum drying methods are adopted in the preparation process, so that the dispersion degree of metal is improved, the stability of the catalyst is enhanced, and the size, the morphology and the crystal face of metal particles can be regulated and controlled. However, the methods have common problems that the preparation steps are more, the conditions are harsh, the industrialization is difficult, and a large amount of organic reagents such as a structure directing agent, a protective agent, an activating agent and the like are required in the preparation process, so that the production cost is increased, and the environmental pollution is easily caused.

Therefore, it is necessary to develop a supported selective hydrogenation catalyst with simple preparation process, environmental protection, low cost and high performance.

Disclosure of Invention

In order to overcome the problems in the prior art, the invention provides a hydrogenation catalyst based on a composite oxide carrier and a preparation method thereof.

The invention aims at providing a hydrogenation catalyst based on a composite oxide carrier, which comprises the composite oxide carrier and an active component loaded on the composite oxide carrier, wherein the composite oxide carrier contains 0.01-3 wt% of halogen elements, the composite oxide is selected from the combination of alumina and other oxides, and the other oxides are selected from at least one of silica, titania, barium oxide and calcium oxide; the active components include a first active component, a second active component, and a third active component.

In a preferred embodiment, the specific surface area of the composite oxide support is 10 to 140m²The water absorption is more than 30%, the bulk density is 0.3-1.0 g/mL, and the pore volume is 0.2-1.2 mL/g.

In a further preferred embodiment, the specific surface area of the composite oxide support is 20 to 100m²(iv) per gram, bulk density of 0.4 to 0.8g/mL, pore volume of 0.35 to 1.00 mL/g.

In a preferred embodiment, the halogen element accounts for 0.01 to 2 wt%, preferably 0.01 to 1 wt% of the total mass of the composite oxide support.

In a further preferred embodiment, the halogen element is selected from fluorine and/or chlorine.

In a preferred embodiment, the shape of the composite oxide support includes, but is not limited to, a powder, a granule, a sphere, a flake, a dentate sphere, a strip, or a strip of clover.

In a preferred embodiment, the mass content of the active component is 0.01-20 wt% and the mass content of the composite oxide carrier is 80-99.9 wt% based on 100 wt% of the mass of the catalyst.

In a further preferred embodiment, the mass content of the active component is 0.01 to 10 wt% and the mass content of the composite oxide support is 90 to 99.9 wt%, based on 100 wt% of the mass of the catalyst.

In a preferred embodiment, the first active component is palladium.

In a further preferred embodiment, the palladium is present in an amount of from 0.005% to 3% by weight, preferably from 0.025% to 1.5% by weight, based on 100% by weight of the mass of the catalyst.

In a preferred embodiment, the second active component is selected from at least one of Ni, Ga, Ag, Bi, Cu, Zn, Ce, In.

In a further preferred embodiment, the second active component is present in an amount of 0.01% to 15% by weight, preferably 0.025% to 1.5% by weight, based on 100% by weight of the mass of the catalyst.

In a preferred embodiment, the third active component is selected from at least one of La, K, Na, Mo.

In a further preferred embodiment, the third active component is present in an amount of 0.01% to 5% by weight, preferably 0.02% to 3% by weight, based on 100% by weight of the mass of the catalyst.

The second purpose of the present invention is to provide a method for preparing a composite oxide support-based hydrogenation catalyst, which comprises the following steps:

(1) mixing powder raw materials, wherein the powder raw materials comprise a composite oxide, a pore-expanding agent and a forming agent;

(2) adding organic matter containing halogen element and acidic aqueous solution;

(3) kneading, molding, granulating, drying and roasting to obtain a composite oxide carrier;

(4) and loading an active component on the composite oxide carrier, and drying and roasting to obtain the catalyst.

In a preferred embodiment, the composite oxide is selected from the group consisting of alumina and other oxides selected from at least one of silica, titania, barium oxide and calcium oxide.

In a further preferred embodiment, the composite oxide is selected from the group consisting of a combination with alumina and titania.

In a further preferred embodiment, the mass ratio of the other oxide to the alumina is (0.2 to 30):100, preferably (0.5 to 15): 100.

In a preferred embodiment, the pore-expanding agent is preferably, but not limited to, at least one selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polypropylene glycol, sesbania powder, carbon black, and white carbon black.

In a further preferred embodiment, the ratio of the amount of the pore-enlarging agent to the mass of the composite oxide is (0.1-8): 100, and preferably (0.2-6): 100.

In a preferred embodiment, the forming agent is at least one selected from the group consisting of polyethylene glycol cellulose, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl methyl cellulose, and starch.

In a more preferred embodiment, the mass ratio of the molding agent to the composite oxide is (0.1-5): 100, preferably (0.2-2): 100, and more preferably (0.3-1): 100.

In a preferred embodiment, the organic material containing a halogen element is selected from an organic material containing a fluorine element and/or an organic material containing a chlorine element.

In a further preferred embodiment, the fluorine-containing organic substance is selected from at least one of trifluoroethanol, tetrafluoropropanol, trifluoroacetal hydrate, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, trifluoropropionic acid, fluoropropanol, difluoropropanol, trifluoropropanol, polytetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene-ethylene copolymer, polyvinyl fluoride; the organic matter containing chlorine element is at least one selected from chloroacetic acid, dichloroacetic acid, trichloroacetic acid, dichloropropionic acid, chloropropanol, trichloroethanol, poly-tetrachloroethylene-ethylene copolymer, polyvinylidene chloride, polyvinyl chloride and trichloroacetic acid.

In a preferred embodiment, the weight ratio of the organic material containing halogen element to the composite oxide is (0.01-3): 100, wherein the amount of the organic material containing halogen element is based on the mass of the halogen element.

In a further preferred embodiment, the weight ratio of the organic material containing halogen element to the composite oxide is (0.01-2): 100, wherein the amount of the organic material containing halogen element is based on the mass of the halogen element.

In a further preferred embodiment, the weight ratio of the organic material containing halogen element to the composite oxide is (0.01-1): 100, wherein the amount of the organic material containing halogen element is based on the mass of the halogen element.

The preparation method has the remarkable characteristic that organic matters containing halogen elements are added in the preparation process, so that the pore structure of the composite oxide carrier can be effectively adjusted. (1) The hydrocarbon component in the organic matter of the halogen can be decomposed to form a large number of micro pores; (2) part of halogen enters an alumina framework, and alumina microcrystal is easily transformed into a flaky shape during high-temperature roasting, so that the pore structure of alumina is influenced, the pore volume is generally promoted to be increased, the specific surface area is increased, and the bulk density is reduced; (3) in addition, part of halogen exists in the carrier in a doped form, the surface acidity of the prepared composite oxide carrier can be influenced by the property of strong electronegativity, and the halogen (especially fluorine atoms and chlorine atoms) on the composite oxide carrier can pull electrons on aluminum atoms and attract electrons of hydroxyl groups around the aluminum atoms, so that the prepared composite oxide carrier is enabled to be in a doped formThe hydrogen protons on the hydroxyl groups are easier to ionize, and the halogen can cause the crystal structure of the carrier to be distorted to cause partial Al-OH polarization, which can promote the surface of the carrierAnd (4) forming acid sites.

Compared with the method that organic matters are added to increase the pore volume and the specific surface area of the composite oxide carrier respectively, inorganic matters added with fluorine and chlorine change the pore structure of alumina, the organic matters added with fluorine and/or chlorine can react with fluorine and/or chlorine elements simultaneously in the high-temperature roasting process of the alumina, so that the composite oxide carrier with better comprehensive performance is prepared, the addition times of the auxiliary agents are reduced, and the forming method is simplified.

In a preferred embodiment, in step (2), the acidic aqueous solution is an aqueous solution containing an organic acid and/or an inorganic acid, preferably an aqueous solution containing an organic acid and an inorganic acid.

In a further preferred embodiment, the organic acid is selected from at least one of oxalic acid, formic acid, acetic acid, citric acid, tartaric acid, preferably from at least one of oxalic acid, citric acid, tartaric acid; the inorganic acid is at least one of nitric acid, sulfuric acid and hydrochloric acid.

In a further preferred embodiment, the concentration of the acidic aqueous solution is 0.005 to 0.5mol/L, preferably 0.01 to 0.2 mol/L.

In a preferred embodiment, in step (3), the drying is performed as follows: drying at 60-160 ℃ for 3-48 h, preferably at 80-120 ℃ for 5-20 h.

In a preferred embodiment, in step (3), the firing is performed as follows: roasting at 400-1500 ℃ for 3-48 h, preferably at 700-1200 ℃ for 5-30 h.

Wherein, the step of drying and roasting is to dry, knead and form the moisture in the green body, the solid phase reaction takes place in the high-temperature roasting process, the powder particles are bonded together, and the composite oxide carrier with certain strength is formed.

In a preferred embodiment, in step (4), a solution containing an active component, preferably including a first active component, a second active component, and a third active component, is sprayed on the composite oxide support.

In a further preferred embodiment, in step (4), the first solution containing the first active component compound, the second solution containing the second active component compound, and the third solution containing the third active component compound are sprayed onto the composite oxide support in three simultaneous sprays or stepwise.

In a preferred embodiment, the first active ingredient compound is at least one selected from the group consisting of palladium chloride, palladium nitrate, and palladium acetate.

In a further preferred embodiment, the first active component compound is used in an amount of 0.005% to 3% by weight, preferably 0.025% to 1.5% by weight, based on 100% by weight of the catalyst, wherein the amount of the first active component-containing compound is based on the content of the first active component (i.e., palladium element) therein.

In a preferred embodiment, the second active component compound is selected from at least one of soluble nitrates, acetates, chlorides of Ni, Ga, Ag, Bi, Cu, Zn, Ce, In.

In a further preferred embodiment, the amount of the second active component-containing compound is 0.01 to 15 wt%, preferably 0.05 to 8 wt%, based on 100 wt% of the catalyst, wherein the amount of the second active component-containing compound is based on the content of the second active component therein.

In a preferred embodiment, the third active ingredient compound is selected from at least one of the soluble nitrates, acetates, chlorides of La, K, Na, Mo.

In a further preferred embodiment, the amount of the third active component-containing compound is 0.01 to 5 wt%, preferably 0.02 to 3 wt%, based on 100 wt% of the catalyst, wherein the amount of the third active component-containing compound is based on the content of the third active component therein.

In a preferred embodiment, in step (4), the drying is performed as follows: drying at 60-160 ℃ for 3-48 h, preferably at 80-120 ℃ for 5-20 h.

In a preferred embodiment, in step (4), the firing is performed as follows: roasting at 300-700 ℃ for 2-48 h, preferably 400-500 ℃ for 3-25 h.

The third object of the present invention is to provide a hydrogenation catalyst based on a composite oxide support obtained by the preparation method according to the second object of the present invention.

The fourth purpose of the invention is to provide the application of the hydrogenation catalyst based on the composite oxide carrier in the acetylene removal reaction of the ethylene raw material gas.

Compared with the prior art, the invention has the following beneficial effects:

(1) the composite oxide carrier adopted by the invention contains halogen elements, so that the acidity and alkalinity, the pore structure and the distribution of active components on the surface of the carrier can be effectively changed;

(2) the preparation method is simple and easy to implement, and is green and environment-friendly;

(3) the catalyst can be used for a carbon dioxide hydrogenation reaction, and has the advantages of high ethylene selectivity, low ethylene loss and low hydrogen consumption while meeting the acetylene hydrogenation removal requirement;

(4) the catalyst works under the conventional hydrogenation operation condition, does not need a specific working condition, and has mild operation condition and flexible process.

Drawings

FIG. 1 shows pyridine adsorption infrared spectra obtained in example 1, comparative examples 1 to 2, and comparative example 8.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

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

[ example 1 ]

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding polytetrafluoroethylene powder accounting for 0.1 percent of the total mass of the oxide powder according to the mass of the element F into the mixed powder obtained in the step 1, fully mixing, and then adding 480mL of aqueous solution containing oxalic acid, nitric acid and acetic acid, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, and the concentration of the acetic acid is 0.025 mol/L;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier A1;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used per 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, after the solution is uniform, the composite oxide carrier A1 obtained in example 1 is quickly soaked and sprayed 6, after drying for 6h at 110 ℃, the composite oxide carrier is roasted for 6h at 440 ℃, and the final catalyst S1 is obtained.

[ example 2 ]

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and trifluoroethanol into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the addition amount of the trifluoroethanol is calculated according to the fact that the mass of the F element accounts for 0.1% of the mass of the oxide powder;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A2.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used per 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the composite oxide carrier A2 obtained in example 2 is quickly soaked and sprayed after the solution is uniform, and the composite oxide carrier A2 is roasted at 440 ℃ for 6 hours after being dried at 110 ℃ to obtain the final catalyst S2.

[ example 3 ]

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding polyvinylidene chloride powder into the mixed powder obtained in the step 1 according to the mass of Cl element which is 0.1 percent of the total mass of the oxide powder, fully mixing, and then adding 480mL of aqueous solution containing oxalic acid, nitric acid and acetic acid, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, and the concentration of the acetic acid is 0.025 mol/L;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A3.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A3 after being uniform, and the composite oxide carrier A3 is roasted for 6 hours at 440 ℃ after being dried for 6 hours at 110 ℃, so that the final catalyst S3 is obtained.

[ example 4 ]

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding polyvinyl chloride powder accounting for 0.1 percent of the total mass of the oxide powder by the mass of Cl element into the mixed powder obtained in the step 1, fully mixing, and then adding 480mL of aqueous solution containing oxalic acid, nitric acid and acetic acid, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, and the concentration of the acetic acid is 0.025 mol/L;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A4.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A4 after being uniform, and the composite oxide carrier A4 is roasted for 6 hours at 440 ℃ after being dried for 6 hours at 110 ℃, so that the final catalyst S4 is obtained.

[ example 5 ]

1. Thoroughly mixing 1000g of alumina powder, 10g of silica powder, 20g of polyvinyl alcohol and 1g of hydroxypropyl cellulose;

2. adding 480mL of aqueous solution containing citric acid, sulfuric acid and tetrafluoropropanol into the mixed powder obtained in the step 1, wherein the concentration of the citric acid is 0.01mol/L, the concentration of the sulfuric acid is 0.1mol/L, and the adding amount of the tetrafluoropropanol is calculated according to the fact that the mass of the F element accounts for 0.01% of the mass of the mixed powder;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A5.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A5 after being uniform, and the composite oxide carrier A5 is calcined at 400 ℃ for 10 hours after being dried at 80 ℃ for 12 hours, so that the final catalyst S5 is obtained.

[ example 6 ]

1. Fully mixing 1000g of alumina powder with 10g of barium oxide powder, 6g of polyethylene glycol, 4g of white carbon black and 2g of hydroxyethyl cellulose;

2. adding 480mL of aqueous solution containing tartaric acid, nitric acid, acetic acid and trifluoroacetic acid into the mixed powder obtained in the step 1, wherein the concentration of the tartaric acid is 0.15mol/L, the concentration of the nitric acid is 0.02mol/L, the concentration of the acetic acid is 0.05mol/L, and the adding amount of the trifluoroethylene is calculated according to the fact that the mass of the F element accounts for 0.5% of the mass of the mixed powder;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A6.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A6 after being uniform, and the composite oxide carrier A6 is roasted for 4 hours at the temperature of 120 ℃ after being dried for 4 hours, so that the final catalyst S6 is obtained.

[ example 7 ]

1. Fully mixing 1000g of aluminum oxide powder, 10g of calcium oxide powder, 5g of polyacrylamide and 10g of polyethylene glycol cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, citric acid and chloroacetic acid into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.02mol/L, the concentration of the nitric acid is 0.005mol/L, the concentration of the citric acid is 0.08mol/L, and the addition amount of the chloroacetic acid is calculated according to the mass of Cl element accounting for 1% of the mass of the mixed powder;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A7.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A7 after being uniform, and the catalyst is roasted for 2 hours at 600 ℃ after being dried for 3 hours at 160 ℃, so that the final catalyst S7 is obtained.

[ example 8 ]

1. Thoroughly mixing 1000g of alumina powder, 10g of silica powder, 2.5g of polypropylene glycol and 22g of carboxymethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid and trichloroethanol into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.03mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the sulfuric acid is 0.02mol/L, and the adding amount of the trichloroethanol is calculated according to the fact that the mass of Cl element accounts for 2% of the mass of the mixed powder;

3. and (3) kneading after the reagents in the step (2) are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain the composite oxide carrier A8.

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier A8 after being uniform, and the composite oxide carrier A8 is roasted for 3 hours at 550 ℃ after being dried for 20 hours at 60 ℃, so that the final catalyst S8 is obtained.

Comparative example 1

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid and acetic acid into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, and the concentration of the acetic acid is 0.025 mol/L;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B1;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B1 after being uniform, and the catalyst D1 is calcined at 440 ℃ for 6 hours after being dried at 110 ℃ to obtain the final catalyst D1.

Comparative example 2

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and potassium fluoride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the potassium fluoride is calculated according to the fact that the mass of the F element accounts for 0.1% of the mass of the mixed powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B2;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B2 after being uniform, and the catalyst D2 is calcined at 440 ℃ for 6 hours after being dried at 110 ℃ to obtain the final catalyst D2.

Comparative example 3

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and ammonium fluoride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the ammonium fluoride is calculated according to the fact that the mass of the element F accounts for 0.1% of the mass of the mixed powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B3;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B3 after being uniform, and the catalyst D3 is obtained after drying for 6h at 110 ℃ and roasting for 6h at 440 ℃.

Comparative example 4

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and potassium fluoride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the potassium fluoride is calculated according to the fact that the mass of the F element accounts for 0.3% of the mass of the oxide powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the length of 2-5mm and the diameter of 1.5mm, drying for 6h at 110 ℃, and roasting for 3h at 1180 ℃ to obtain a composite oxide carrier B4;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the using amounts of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate are respectively calculated according to the mass content of Pd, Ag, K and La in the catalyst, wherein the Pd is 0.03%, the Ag is 0.04%, the K is 0.5% and the La is 0.05%, the composite oxide carrier B4 is quickly soaked and sprayed after the solution is uniform, and the final catalyst D4 is obtained by drying the composite oxide carrier B4 for 6 hours at 110 ℃ and then roasting the composite oxide carrier B for 6 hours at 440 ℃.

Comparative example 5

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and potassium fluoride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the potassium fluoride is calculated according to the fact that the mass of the F element accounts for 0.01% of the mass of the oxide powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B5;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B5 after being uniform, and the catalyst D5 is obtained after drying for 6h at 110 ℃ and roasting for 6h at 440 ℃.

Comparative example 6

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and potassium chloride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the potassium chloride is calculated according to the mass of Cl element accounting for 0.1% of the mass of the oxide powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B6;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B6 after being uniform, and the catalyst D6 is obtained after drying for 6h at 110 ℃ and roasting for 6h at 440 ℃.

Comparative example 7

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of aqueous solution containing oxalic acid, nitric acid, acetic acid and ammonium chloride into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, and the adding amount of the ammonium chloride is calculated according to the fact that the mass of Cl element accounts for 0.1% of the mass of the oxide powder;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B7;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B7 after being uniform, and the catalyst D7 is obtained after drying for 6h at 110 ℃ and roasting for 6h at 440 ℃.

Comparative example 8

1. Fully mixing 1000g of alumina powder with 10g of titanium oxide powder, 5g of sesbania powder, 3g of carbon black and 3g of ethyl cellulose;

2. adding 480mL of an aqueous solution containing potassium fluoride, ethyl acetate, oxalic acid, nitric acid and acetic acid into the mixed powder obtained in the step 1, wherein the concentration of the oxalic acid is 0.015mol/L, the concentration of the nitric acid is 0.03mol/L, the concentration of the acetic acid is 0.025mol/L, the adding amount of the potassium fluoride is calculated according to that the mass of the F element accounts for 0.1% of the mass of the oxide powder, and the adding amount of the ethyl acetate is equal to the molar amount of the trifluoroethanol added in the example 2;

3. kneading after the reagents in the step 2 are fully dissolved and stabilized, extruding and cutting into particles with the diameter of 1.5mm and the length of 2-5mm, drying at 110 ℃ for 6h, and roasting at 1180 ℃ for 3h to obtain a composite oxide carrier B8;

4. 48mL of aqueous solution containing palladium nitrate, silver nitrate, potassium nitrate and lanthanum nitrate is used for every 100g of composite oxide carrier, the dosage of the palladium nitrate, the silver nitrate, the potassium nitrate and the lanthanum nitrate is respectively calculated according to the mass content of Pd, Ag, K and La elements in the catalyst, wherein the Pd is 0.03 percent, the Ag is 0.04 percent, the K is 0.5 percent and the La is 0.05 percent, the solution is quickly soaked and sprayed on the composite oxide carrier B8 after being uniform, and the catalyst D8 is calcined at 440 ℃ for 6 hours after being dried at 110 ℃ to obtain the final catalyst D8.

[ Experimental example 1 ]

The results of pyridine adsorption infrared tests on the catalysts obtained in example 1, comparative examples 1 to 2 and comparative example 8 are shown in fig. 1, wherein a fluorine-containing organic substance is added in the preparation process of example 1, a fluorine-containing substance is not added in the preparation process of comparative example 1, and a fluorine-containing inorganic substance is added in the preparation processes of comparative examples 2 and 8.

As can be seen from FIG. 1, the catalyst obtained in example 1 contained not only at 1448cm^-1、1610cm^-1The nearby L acid site also contains a DNA fragment located at 1540cm^-1And 1645cm^-1Nearby B acid sites. In the catalyst obtained in comparative example 1, only the L acid site was contained. The catalysts obtained in comparative examples 2 and 8 contained L acid sites and B acid sites, but the absorption peak intensity of the B acid sites was significantly weaker than that of the catalysts obtained in comparative examples 2 and 8

Example 1, which shows that the content of B acid sites is significantly lower than the content of B acid sites in the catalyst obtained in example 1.

[ Experimental example 2 ]

The intermediate product composite oxide supports prepared before the active components were loaded in the above examples and comparative examples were subjected to measurement of specific surface area, bulk density and pore volume. Wherein the specific surface area is measured by adopting a nitrogen physical adsorption BET method; the bulk density is calculated by measuring the mass of 100mL of the composite oxide carrier, and the pore volume is measured by a mercury intrusion method, which is referred to a common composite oxide carrier pore volume measurement method. The measurement results are shown in Table 1.

Table 1:

numbering	Specific surface area (m)2/g)	Bulk density (g/mL)	Pore volume (mL/g)
				A1	35.8	0.58	0.58
A2	36.7	0.60	0.66
				A3	32.1	0.52	0.59
A4	33.2	0.53	0.60
				B1	20.7	0.65	0.33
B2	23.9	0.66	0.39
				B3	28.3	0.73	0.47
B4	24.9	0.77	0.45
				B5	26.6	0.68	0.38
B6	24.2	0.75	0.43
				B7	27.7	0.75	0.48
B8	26.8	0.67	0.51

From table 1, it can be found that the composite oxide carrier prepared by the method of the present invention has a high specific surface area and pore volume, which is advantageous for the preparation of the supported metal catalyst; and because the bulk density is lower, the dosage of the corresponding catalyst can be reduced under the condition of the same filling volume.

[ Experimental example 3 ]

The selective hydrogenation performance of ethylene is evaluated for catalysts S1-S4 and D1-D8 by the following method:

1mL of the catalyst was loaded into a stainless steel reactor having an inner diameter of 7.8mm, purged with nitrogen, and then reduced at 180 ℃ for 1 hour with hydrogen.

The ethylene raw material gas with simulated hydrogenation conditions is mixed with hydrogen and then is introduced into a reactor, and the raw material gas comprises the components of 0.4 mol% of acetylene, 6 mol% of ethane, 93.6 mol% of ethylene, 1.6 mol% of hydrogen-acetylene ratio and 10000h of space velocity^-1. The reaction temperature range is 60-120 ℃, the catalytic performance of the catalyst is tested and evaluated at intervals of 10 ℃, the acetylene conversion rate and the ethylene selectivity are calculated,

the ethylene conversion (C) and selectivity (S) were calculated as:

the activity of the catalyst is expressed in terms of acetylene conversion at 90 ℃ and ethylene selectivity with complete removal of acetylene. The test results are shown in Table 2.

TABLE 2

Catalyst and process for preparing same	Conversion (%)	Selectivity (%)
			S1	100	51.6
S2	99.8	50.5
			S3	99.9	49.8
S4	99.8	48.2
			D1	98.9	32.5
D2	99.2	37.3
			D3	99.5	40.6
D4	98.7	38.7
			D5	98.5	36.2
D6	99.4	35.6
			D7	99.1	39.1
D8	98.8	40.1

As can be seen from Table 2, the catalyst prepared by the method of the present invention has better activity and selectivity (especially selectivity) than the catalyst prepared by the comparative example.