阅读说明：本技术 一种乙烯氧氯化催化剂及其制备方法和应用 (Ethylene oxychlorination catalyst and preparation method and application thereof ) 是由 穆晓蕾 贾春革 李斗星 齐兰芝 于 2020-05-15 设计创作，主要内容包括：本发明涉及催化剂领域的一种乙烯氧氯化催化剂及其制备方法和应用。所述乙烯氧氯化催化剂,包括载体以及负载在所述载体上的活性组分；其中,所述载体为球状介孔载体；所述活性组分包含主活性组分铜组分、助活性组分；所述助活性组分包含碱金属组分和稀土金属组分。本发明制得的催化剂具有较高的比表面积、孔容以及相对集中的孔径分布,在活性组分负载量很低的情况下,就能够达到较好的催化活性、选择性和高收率。(The invention relates to an ethylene oxychlorination catalyst and a preparation method and application thereof, belonging to the field of catalysts. The ethylene oxychlorination catalyst comprises a carrier and an active component loaded on the carrier; wherein the carrier is a spherical mesoporous carrier; the active component comprises a main active component copper component and an auxiliary active component; the co-active component comprises an alkali metal component and a rare earth metal component. The catalyst prepared by the invention has higher specific surface area, pore volume and relatively concentrated pore size distribution, and can achieve better catalytic activity, selectivity and high yield under the condition of very low active component loading.)

1. An ethylene oxychlorination catalyst characterized by: the catalyst comprises a carrier and an active component loaded on the carrier;

wherein the carrier is a spherical mesoporous carrier;

the active component comprises a main active component copper component and an auxiliary active component;

the co-active component comprises an alkali metal component and a rare earth metal component.

2. The ethylene oxychlorination catalyst according to claim 1, wherein:

the carrier is a spherical mesoporous alumina carrier;

the average particle size of the catalyst is 20-80 μm, preferably 30-70 μm;

the specific surface area of the catalyst is 400-600 m²Per g, preferably 500 to 600m²/g。

3. The ethylene oxychlorination catalyst according to claim 2, wherein:

the pore volume of the catalyst is 0.3-1.2 ml/g, preferably 0.6-1.0 ml/g;

the most probable pore diameter of the catalyst is 3-18 nm, and preferably 3-12 nm.

4. The ethylene oxychlorination catalyst according to claim 1, wherein:

the copper component is selected from water-soluble copper salts;

the rare earth metal component is selected from water-soluble rare earth metal salts;

the alkali metal component is selected from alkali metal salts.

5. The ethylene oxychlorination catalyst according to claim 1, wherein:

the rare earth metal is selected from at least one of lanthanum, cerium, neodymium, praseodymium and yttrium;

the alkali metal is at least one selected from potassium, lithium, rubidium and cesium.

6. An ethylene oxychlorination catalyst according to any one of claims 1 to 5, wherein:

based on the total weight of the carrier being 100%, the content of the main active component copper component is 1-10 wt%, preferably 1.5-3 wt% calculated by metal elements; the content of the alkali metal component is 0.1-10 wt% calculated by metal elements, preferably 0.5-1 wt%; the content of the rare earth metal component is 0.1-10 wt% calculated by metal elements, and preferably 0.5-1 wt%.

7. A process for the preparation of an ethylene oxychlorination catalyst according to any one of claims 1 to 6, characterized by comprising the steps of:

preparing the spherical mesoporous alumina carrier, soaking the spherical mesoporous alumina carrier in a solution containing an active component, and drying to obtain the ethylene oxychlorination catalyst.

8. The process for the preparation of an ethylene oxychlorination catalyst according to claim 7, wherein:

the preparation method of the spherical mesoporous alumina carrier comprises the following steps:

(1) mixing an aluminum source and an acid solution until the aluminum source and the acid solution are completely dissolved to obtain a solution A;

(2) mixing a template agent and an acid solution until a solid is completely dissolved to obtain a solution B;

(3) mixing the solution A and the solution B, adding an additive, adjusting the pH value, and sequentially aging, filtering, washing and drying to obtain mesoporous alumina material raw powder;

(4) and (4) removing the template agent in the product obtained in the step (3) to obtain the spherical mesoporous alumina carrier.

9. A process for the preparation of an ethylene oxychlorination catalyst according to claim 8, wherein:

the molar ratio of the amounts of the template agent, the aluminum source and the hydrochloric acid to the amounts of the hydrogen chloride, the nitric acid and the water is 1: (80-180): (350-600): (50-150): (20000 to 30000); preferably 1: (100-120): (400-500): (80-100): (25000 to 30000).

10. A process for the preparation of an ethylene oxychlorination catalyst according to claim 8, wherein:

the template agent is triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide;

and/or the presence of a gas in the gas,

the aluminum source is at least one selected from aluminum isopropoxide, sodium metaaluminate and aluminum nitrate.

11. A process for the preparation of an ethylene oxychlorination catalyst according to claim 8, wherein:

in the step (1), the acid in the step (1) is nitric acid; the dissolving temperature is 60-80 ℃;

and/or the presence of a gas in the gas,

in the step (2), the acid in the step (2) is hydrochloric acid; the dissolving temperature is 20-60 ℃, and preferably 40-50 ℃.

12. A process for the preparation of an ethylene oxychlorination catalyst according to claim 8, wherein:

in the step (3), the amount of the additive is 1.0-3.0 wt% based on the total mass of the carrier;

the additive is selected from one or more of ionic surfactant, nonionic surfactant and amphoteric surfactant;

and adjusting the pH value to 6.0-8.0.

13. A process for the preparation of an ethylene oxychlorination catalyst according to claim 8, wherein:

in the step (3), a mixture of water and ethanol is adopted for washing, and the volume ratio of the water to the ethanol is 1: (0.1 to 10.0), preferably 1: (0.5 to 2.0);

and/or the presence of a gas in the gas,

in the step (4), the template removal process comprises: roasting for 1-10 h at the temperature of 400-1000 ℃; preferably 400-600 ℃, and roasting for 2-5 h.

14. The process for the preparation of an ethylene oxychlorination catalyst according to claim 7, wherein:

the active component-containing solution contains a solution of a copper component, an alkali metal component, and a rare earth metal component.

15. An ethylene oxychlorination catalyst prepared according to the preparation process of any one of claims 7 to 14.

16. Use of a catalyst according to any one of claims 1 to 6 or 15 in an oxychlorination reaction of ethylene.

17. A method for preparing dichloroethane, comprising: reacting ethylene, hydrogen chloride and oxygen in the presence of the catalyst of any one of claims 1 to 6 or 15 under ethylene oxychlorination reaction conditions;

preferably, the oxychlorination reaction conditions include: the temperature is 190-250 ℃; the reaction pressure is 0.15-0.7 MPa; the mol ratio of the ethylene to the hydrogen chloride to the oxygen is 1 (1.8-2) to 0.5-0.6.

Technical Field

The invention relates to the field of catalysts, and in particular relates to an ethylene oxychlorination catalyst and a preparation method and application thereof.

Background

1, 2-dichloroethane, commonly known as dichloroethane (EDC), is a very important industrial chemical raw material, and after the dichloroethane is cracked, it is converted into vinyl chloride and hydrogen chloride, and the vinyl chloride monomer can be polymerized into polyvinyl chloride (PVC) with wide application. The hydrogen chloride obtained from the cracking is separated from the vinyl chloride and then brought into contact with ethylene and an oxygen-containing gas in the presence of a catalyst for the production of EDC, i.e. oxychlorination.

Catalysts and processes for the production of chlorinated hydrocarbons by oxychlorination processes have been developed over the years. Specifically, a process for producing 1, 2-dichloroethane by oxychlorination using oxygen, hydrogen chloride and ethylene in the presence of a catalyst has been widely used in industrial facilities around the world. Since the oxychlorination reaction is exothermic, it is advantageous to use a fluidized bed process, i.e. a gas phase reaction of a mixture of ethylene, hydrogen chloride and oxygen or an oxygen-containing gas in a fluidized bed, in order to remove the heat of reaction in time. At present, two different production methods are industrially used according to the raw material route: one is an air process represented by b.f. goodrich company in the united states, which performs an oxychlorination reaction using air, ethylene and hydrogen chloride as raw materials, and the other is an oxygen process represented by mitsui pressure ltd.

Catalysts have been used successfully in the production of chlorinated hydrocarbons by oxychlorination for many years. Representative catalysts include about 4 to 17 weight percent copper catalyst. A typical copper compound is copper chloride, which is deposited on a support such as alumina, silica, diatomaceous earth, and the like.

The ethylene oxychlorination catalyst can be prepared by two methods, namely an impregnation method and a coprecipitation method, according to different preparation methods of the catalyst.

The dipping method is to dip the carrier with certain physical property and particle size into the solution of active component of the catalyst, stir evenly, dry and calcine to prepare the catalyst. The catalyst prepared by the impregnation method is simple, and the carrier is a main component and plays an important role in improving the activity, selectivity, mechanical strength and thermal stability of the catalyst.

The coprecipitation method for preparing the catalyst is to carry out coprecipitation reaction on an active component and a carrier to prepare a gel-like coprecipitate, and then the gel-like coprecipitate is subjected to spray drying and molding to prepare the catalyst with certain viscosity and certain force distribution. The catalyst prepared by the method has uniform mixture of the active component and the carrier, does not have the phenomenon of falling off of the active component, and does not need to pretreat the carrier.

JP-A No. 45-39616 discloses a method for producing a fluidized bed oxychlorination catalyst by a coprecipitation method. The method takes hydrochloric acid solution of copper chloride and sodium metaaluminate as raw materials, and prepares a gelatinous coprecipitate through coprecipitation reaction, and then prepares the catalyst after aging, slurrying, spray drying and forming, washing and roasting. However, the catalyst is slightly acidic and corrodes the reactor. Chinese patent CN1114594A improves the above method and proposes a method of washing with alkaline solution, so the prepared catalyst has the advantages of neutrality and no corrosion to equipment. However, the catalysts prepared by the two patents use single copper chloride as an active component, and when the catalyst is used for ethylene oxychlorination reaction, copper chloride loss occurs under high-temperature reaction conditions, the catalyst is sticky due to copper chloride precipitation, the fluidization condition of the catalyst is poor, and the selectivity is reduced. In order to overcome the defect of single copper chloride component, the ethylene oxychlorination catalyst prepared by an impregnation method, such as CN1054764A, CN100457260A and the like, is added with auxiliary active components such as alkali metal, rare earth metal and the like on the basis of taking copper chloride as a main active component, thereby improving the flowing state of the catalyst and improving the selectivity of the catalyst, but the specific surface area is lower, the pore size distribution is not concentrated, and the addition amount of the active component is higher.

In the research, the common carrier of the prior oxychlorination catalyst has low specific surface area and non-concentrated pore size distribution, and is not beneficial to the dispersion of active metal components on the surface of the carrier and the diffusion of raw materials and products in the reaction process. Therefore, how to further improve the reaction performance of the ethylene oxychlorination catalyst is a problem to be solved urgently.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides an ethylene oxychlorination catalyst. In particular to an ethylene oxychlorination catalyst and a preparation method and application thereof. The invention aims to overcome the defects of uneven dispersion of active components and poor catalytic activity of the existing ethylene oxychlorination catalyst, and provides a method for preparing the ethylene oxychlorination catalyst and application of the catalyst prepared by the method in ethylene oxychlorination reaction. The catalyst prepared by the invention has higher specific surface area, pore volume and relatively concentrated pore size distribution, and can achieve better catalytic activity, selectivity and high yield under the condition of very low active component loading.

One of the objects of the present invention is to provide an ethylene oxychlorination catalyst comprising a carrier and an active component supported on the carrier;

wherein, the active component can comprise a main active component copper component and an auxiliary active component;

the co-active component comprises an alkali metal component and a rare earth metal component.

The average particle size of the catalyst can be 20-80 μm, and preferably 30-70 μm;

the specific surface area of the catalyst can be 400-600 m²Per g, preferably 500 to 600m²/g；

The pore volume of the catalyst can be 0.3-1.2 ml/g, preferably 0.6-1.0 ml/g;

the most probable pore diameter of the catalyst can be 3-18 nm, and preferably 3-12 nm.

The carrier can be a spherical mesoporous carrier, in particular a spherical mesoporous alumina carrier; the spherical mesoporousThe average particle size of the alumina carrier is 20-80 μm, preferably 30-70 μm, and the specific surface area of the carrier is 400-700 m²Preferably 450 to 600 m/g²The pore volume is 0.3-1.5 ml/g, preferably 0.6-1.5 ml/g, and the most probable pore diameter is 3-20 nm, preferably 3-18 nm.

The content of the main active component copper component can be 1 to 10 wt%, preferably 1.5 to 3 wt% calculated by the total weight of the carrier as 100% by weight; the content of the alkali metal component can be 0.1-10 wt% calculated by metal elements, and is preferably 0.5-1 wt%; the content of the rare earth metal component can be 0.1-10 wt%, preferably 0.5-1 wt% calculated by metal elements.

The rare earth metal can be selected from at least one of lanthanum, cerium, neodymium, praseodymium and yttrium;

the alkali metal may be selected from at least one of potassium, lithium, rubidium, and cesium.

In particular, the copper component may be selected from water-soluble copper salts; specific types of metal salts such as sulfate, nitrate, and chloride, preferably chloride;

the rare earth metal component may be selected from water-soluble rare earth metal salts; the water-soluble rare earth metal salt may be at least one of carbonate, hydrochloride (chloride), bromide and nitrate of rare earth metal, preferably chloride;

the alkali metal component may be selected from alkali metal salts; the alkali metal salt may be specifically selected from at least one of sulfate, carbonate, nitrate, and hydrochloride (chloride) of an alkali metal; preferably carbonates and/or chlorides; more preferably chloride.

Another object of the present invention is to provide a method for preparing the ethylene oxychlorination catalyst, which comprises the following steps:

preparing the spherical mesoporous alumina carrier, then dipping the spherical mesoporous alumina carrier in a solution containing active components, and drying to obtain the ethylene oxychlorination catalyst.

In particular, the amount of the solvent to be used,

the preparation method of the spherical mesoporous alumina carrier comprises the following steps:

(1) mixing an aluminum source and an acid solution until the aluminum source and the acid solution are completely dissolved to obtain a solution A;

(2) mixing a template agent and an acid solution until a solid is completely dissolved to obtain a solution B;

(3) mixing the solution A and the solution B, adding an additive, adjusting the pH value to 6.0-8.0, and sequentially aging, filtering, washing and drying to obtain mesoporous alumina material raw powder;

(4) and (4) removing the template agent in the product obtained in the step (3) to obtain the spherical mesoporous alumina carrier.

Wherein the content of the first and second substances,

the dosage of the template agent, the aluminum source and the hydrogen chloride and the nitric acid in the hydrochloric acid can be selected and adjusted in a wide range. Preferably, the molar ratio of the amounts of the template agent, the aluminum source and the hydrogen chloride, the nitric acid and the distilled water in the hydrochloric acid can be 1: (80-180): (350-600): (50-150): (20000 to 30000); preferably 1: (100-120): (400-500): (80-100): (25000 to 30000).

According to the invention, in order to enable the obtained mesoporous alumina raw powder to have a regular and ordered pore channel distribution structure, the template agent can be selected from triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide. The template product is specifically purchased from Aldrich company under the trade name P123, the molecular formula is EO20PO70EO20, and the average molecular weight Mn is 5800.

The aluminum source may be various aluminum sources conventionally used in the art, such as aluminum isopropoxide, sodium metaaluminate, aluminum nitrate, etc., preferably aluminum isopropoxide.

According to the present invention, there is provided,

in the step (1), the acid in the step (1) is nitric acid; the dissolution temperature can be 60-80 ℃. In the specific operation, in the step (1), an aluminum source is added into nitric acid, and the mixture is placed in a water bath at the temperature of 60-80 ℃ and kept at the constant temperature until the solid is fully dissolved. In order to further facilitate uniform mixing between the substances, the aluminum source and the nitric acid are preferably mixed under stirring conditions.

In the step (2), the acid in the step (2) is hydrochloric acid; the dissolving temperature can be 20-60 ℃, and preferably 40-50 ℃. To further facilitate uniform mixing between the substances, the dissolution of the templating agent in hydrochloric acid is preferably carried out with stirring until the solid substances are completely dissolved.

In the step (3), the amount of the additive is 1.0-3.0 wt% based on the total mass of the carrier. In order to better adjust the pore size of the carrier, the additive is introduced as a structure directing agent, so that the additive is firmly connected to the surface of the carrier, and the phenomenon that the carrier is subjected to hard agglomeration on the surface during subsequent high-temperature roasting is avoided, so that the performance of the carrier is reduced, and the activity is reduced. The additive can be one or more of various existing ionic surfactants, nonionic surfactants and amphoteric surfactants. Preferred are cationic surfactants or nonionic surfactants such as ammonium salt type cationic surfactants, quaternary ammonium salt type cationic surfactants, polyethylene glycol type nonionic surfactants and the like.

In the step (3), the pH value of the mixed solution is adjusted to 6.0-8.0 by adding alkali liquor, wherein the alkali liquor can be various substances or mixtures which are conventionally used for adjusting the pH value, and NaOH is preferred.

In the step (3), after the precipitate is separated out, the aging needs to be continued for 1-48 hours, preferably 24-36 hours.

In the step (3), the filtration and washing methods are well known in the art. In a specific embodiment of the invention, the method of filtering and washing comprises: filtering by using a laboratory suction filtration method, and repeatedly washing by using a mixture of water and ethanol until the conductivity of the clear liquid after washing is lower than 30 mu S/cm. Wherein the volume ratio of water to ethanol is 1: (0.1 to 10.0), preferably 1: (0.5-2.0).

In the step (3), the drying manner is preferably spray drying, and the spray drying may be performed according to a conventional manner, and may be at least one selected from the group consisting of pressure spray drying, centrifugal spray drying, and pneumatic spray drying. The temperature of the spray drying is 80-120 ℃, and preferably 100-110 ℃.

In the step (4), the removal process of the template agent comprises the following steps: roasting for 1-10 h at the temperature of 400-1000 ℃; preferably 400-600 ℃, and roasting for 2-5 h.

According to the invention, the active component loaded on the spherical mesoporous alumina carrier can be subjected to impregnation treatment in a solution containing the active component in an impregnation mode, the metal component enters a pore channel by virtue of capillary pressure of a pore channel structure of the carrier until adsorption balance is achieved, and the ethylene oxychlorination catalyst is obtained after drying. The impregnation process is carried out at normal temperature. The drying process can be carried out in a drying box under the following drying conditions: the temperature is 90-180 ℃, preferably 100-150 ℃, and the time is 1-8 hours, preferably 3-5 hours.

Wherein the solution containing the active components comprises a main active component copper component, an auxiliary active component alkali metal component and a solution of a rare earth metal component.

Wherein, the auxiliary active component rare earth metal is selected from at least one of lanthanum, cerium, neodymium, praseodymium and yttrium, and is preferably cerium; the auxiliary active component alkali metal is at least one selected from potassium, lithium, rubidium and cesium, and potassium is preferred;

according to the invention, both the main and the co-active components of the catalyst for the oxychlorination of ethylene are present in the form of metal salts, for example of the sulphate, nitrate and chloride type, preferably in the form of chloride.

Based on the weight of the carrier, the content of the main active component copper component is 1-10 wt%, preferably 1.5-3 wt% calculated by metal elements; the content of the rare earth metal component is 0.1-10 wt% calculated by metal elements, preferably 0.5-1 wt%; the content of the alkali metal component is 0.1-10 wt%, preferably 0.5-1 wt% calculated by metal elements.

More specifically, the preparation method comprises the following steps:

it is a first object of the present invention to provide a process for the preparation of an ethylene oxychlorination catalyst, the process comprising the steps of:

(1) mixing an aluminum source and a nitric acid solution until the aluminum source and the nitric acid solution are completely dissolved to obtain a solution A;

(2) mixing a template agent and a hydrochloric acid solution until a solid is completely dissolved to obtain a solution B;

(3) mixing the solution A and the solution B, adding a surfactant, adjusting the pH value to 6.0-8.0, and sequentially aging, filtering, washing and drying to obtain mesoporous alumina material raw powder;

(4) removing the template agent in the product obtained in the step (3) to obtain a spherical mesoporous alumina carrier;

(5) and (4) dipping the spherical mesoporous alumina carrier obtained in the step (4) in a solution containing a main active component Cu, an auxiliary active component alkali metal and a rare earth metal, and drying to obtain the ethylene oxychlorination catalyst.

The reactor or the reaction apparatus used in the production method of the present invention is a reactor or a reaction apparatus which is generally used in the prior art.

The invention also aims to provide the ethylene oxychlorination catalyst prepared by the preparation method.

The fourth purpose of the invention is to provide the ethylene oxychlorination catalyst and the application of the catalyst prepared by the method in the ethylene oxychlorination reaction.

The fifth purpose of the invention is to provide a method for preparing dichloroethane, which comprises the following steps: under the condition of ethylene oxychlorination reaction, ethylene, hydrogen chloride and oxygen are reacted in the presence of the catalyst to prepare dichloroethane.

The specific method can be as follows: introducing ethylene, oxygen and hydrogen chloride into a fluidized bed reactor in the presence of a catalyst to perform oxychlorination, wherein the catalyst is the ethylene oxychlorination catalyst prepared by the method.

The oxychlorination reaction conditions may include: the temperature is 190-250 ℃, preferably 200-240 ℃, and more preferably 225-235 ℃; the reaction pressure is 0.15-0.7 MPa, preferably 0.25-0.5 MPa, and more preferably 0.32-0.38 MPa; the mol ratio of the ethylene to the hydrogen chloride to the oxygen is 1 (1.8-2) to 0.5-0.6.

The structure of the catalyst carrier (including physical structures such as specific surface area, pore volume, pore size distribution and the like and chemical structures such as surface acid sites, electronic properties and the like) not only has important influence on the dispersion degree of the active metal components, but also directly influences mass transfer and diffusion in the reaction process. Therefore, the catalytic performances of the catalyst, such as activity, selectivity and stability, depend on the catalytic characteristics of the active components and are related to the characteristics of the catalyst carrier. Most of the commercial activated alumina at present has small specific surface area and pore volume, and the pore channel distribution is not concentrated and disordered. The use of the alumina as a carrier for preparing the ethylene oxychlorination catalyst is not beneficial to the distribution of active components and reduces the activity of the catalyst.

Compared with the prior art, the ethylene oxychlorination catalyst prepared by the method provided by the invention has the following advantages:

(1) the ethylene oxychlorination catalyst prepared by the method provided by the invention can achieve better catalytic activity and selectivity under the condition of very low load of main active components, can effectively reduce the preparation cost of the ethylene catalyst and has more economic benefits;

(2) the ethylene oxychlorination catalyst prepared by the method provided by the invention has the characteristics of higher specific surface area and pore volume, regular and ordered pore channel structure, concentrated pore size distribution and the like, so that the dispersion degree of the loaded active components is higher, the contact between active site positions and a substrate is increased, and the transmission of reactants is facilitated;

(3) the ethylene oxychlorination catalyst prepared by the method provided by the invention shows good catalytic performance when used in ethylene oxychlorination reaction, and has high hydrogen chloride conversion rate, high ethylene selectivity and high product yield.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.

In the following examples and comparative examples, the starting materials used are commercially available.

Sources of raw materials for this application

Aluminum isopropoxide: purchased from ALDRICH, with a purity of greater than 99%.

Template P123: purchased from ALDRICH under the trade name P123 and having the molecular formula

EO20PO70EO20, average molecular weight Mn 5800.

Polyethylene glycol laurate, available from carbofuran technologies ltd, with a purity greater than 99%.

Copper chloride: purchased from Yongda reagent and analyzed.

Potassium chloride: purchased from Beijing Qingke Kai Huafeng scientific and technological development Co., Ltd, and analyzed.

Cerium chloride: purchased from Innochem and having a purity of more than 99 percent.

In the following examples and comparative examples, the specific surface area and pore size of a sample were measured using a Quadrasorb SI model specific surface instrument, wherein the specific surface area was calculated using the BET equation for adsorption data with a relative pressure in the range of 0.05 to 0.25, and the pore volume and pore size were calculated using the BJH model for desorption curve data on isotherms; the particle size distribution of the sample is carried out on a Malvern laser particle sizer; analysis of the reaction product composition was performed on an agilent 3800 gas chromatograph.

Example 1

7g of aluminum isopropoxide was added to a solution containing 90ml of water and 1.5g of nitric acid, and stirred at 60 ℃ until completely dissolved to obtain a solution A. 2g of template P123 was added to a solution of 12g of 37% hydrochloric acid and 70ml of water, and the mixture was stirred at 50 ℃ until P123 was completely dissolved to obtain solution B. And mixing the solution A and the solution B, slowly adding 0.03g of polyethylene glycol laurate while stirring, adjusting the pH value to 6.0-8.0 by using NaOH, and aging for 24 hours at room temperature. And (3) mixing the obtained product by using a volume ratio of 1: 1, repeatedly washing until the conductivity of the clear liquid after washing is lower than 30 mu S/cm. Then spray drying is carried out at 100 ℃ to obtain the mesoporous alumina raw powder. Roasting the mesoporous alumina raw powder at 600 ℃ for 2h, and removing the template agent to obtain the spherical mesoporous alumina carrier 1.

Dissolving a certain amount of copper chloride, potassium chloride and cerium chloride in deionized water, impregnating a carrier, and drying at 120 ℃ for 3 hours to obtain the ethylene oxychlorination catalyst 1 containing 3 wt% of copper, 1 wt% of potassium and 1 wt% of cerium, wherein the mass of the carrier is 100%.

The pore structure parameters of the spherical mesoporous alumina support 1 and the ethylene oxychlorination catalyst 1 are shown in table 1.

Example 2

10g of aluminum isopropoxide was added to a solution containing 100ml of water and 3g of nitric acid, and stirred at 80 ℃ until completely dissolved to obtain a solution A. 2g of template P123 was added to a solution of 20g of 37% hydrochloric acid and 70ml of water, and the mixture was stirred at 35 ℃ until the P123 was completely dissolved to obtain solution B. And mixing the solution A and the solution B, slowly adding 0.07g of polyethylene glycol laurate while stirring, adjusting the pH value to 6.0-8.0 by using NaOH, and aging for 30 hours at room temperature. And (3) mixing the obtained product by using a volume ratio of 1: and repeatedly washing the mixed solution of water and ethanol with 0.5 until the conductivity of the clear liquid is lower than 30 mu S/cm after washing. Then spray drying is carried out at 100 ℃ to obtain the mesoporous alumina raw powder. And roasting the mesoporous alumina raw powder at 500 ℃ for 4h, and removing the template agent to obtain the spherical mesoporous alumina carrier 2.

Dissolving a certain amount of copper chloride, potassium chloride and cerium chloride in deionized water, impregnating a carrier, and drying at 120 ℃ for 3 hours to obtain the ethylene oxychlorination catalyst 2 containing 2 wt% of copper, 0.5 wt% of potassium and 0.5 wt% of cerium, wherein the mass of the carrier is 100%.

The pore structure parameters of the spherical mesoporous alumina support 2 and the ethylene oxychlorination catalyst 2 are shown in table 1.

Example 3

12g of aluminum isopropoxide was added to a solution containing 105ml of water and 3g of nitric acid, and stirred at 60 ℃ until completely dissolved to obtain a solution A. 2g of template P123 was added to a solution of 15g of 37% hydrochloric acid and 70ml of water, and the mixture was stirred at 50 ℃ until P123 was completely dissolved to obtain solution B. And mixing the solution A and the solution B, slowly adding 0.03g of polyethylene glycol laurate while stirring, adjusting the pH value to 6.0-8.0 by using NaOH, and aging for 36 hours at room temperature. And (3) mixing the obtained product by using a volume ratio of 1: 2, repeatedly washing the mixed solution of water and ethanol until the conductivity of the clear liquid after washing is lower than 30 mu S/cm. Then spray drying is carried out at 110 ℃ to obtain the mesoporous alumina raw powder. Roasting the mesoporous alumina raw powder at 400 ℃ for 5h, and removing the template agent to obtain the spherical mesoporous alumina carrier 3.

Dissolving a certain amount of copper chloride, potassium chloride and cerium chloride in deionized water, impregnating a carrier, and drying at 120 ℃ for 3 hours to obtain the ethylene oxychlorination catalyst 3 containing 1.5 wt% of copper, 0.5 wt% of potassium and 1 wt% of cerium, wherein the mass of the carrier is 100%.

The pore structure parameters of the spherical mesoporous alumina support 3 and the ethylene oxychlorination catalyst 3 are shown in table 1.

Example 4

A support was prepared as in example 1, and then amounts of copper chloride, rubidium chloride and lanthanum chloride were dissolved in deionized water, the support was impregnated, and dried at 120 ℃ for 3 hours to give an ethylene oxychlorination catalyst 4 containing 1.5 wt% of copper, 0.5 wt% of rubidium and 1 wt% of lanthanum, based on 100% by mass of the support. The pore structure parameters of the ethylene oxychlorination catalyst 4 are shown in table 1.

Example 5

A catalyst was prepared as in example 1 except that N, N-dimethylethylenediamine was used instead as an additive to obtain a support 5 and an ethylene oxychlorination catalyst 5, respectively.

Comparative example 1

A catalyst was prepared in the same manner as in example 1 except that commercially available activated alumina was directly used as a support, thereby obtaining a support 6 and an ethylene oxychlorination catalyst 6, respectively.

Comparative example 2

The support and the ethylene oxychlorination catalyst were prepared in the same manner as in example 1, without adding an additive during the preparation of the support, to thereby obtain a support 7 and an ethylene oxychlorination catalyst 7, respectively.

Application example 1

Respectively taking 70g of catalyst 1-7, filling the catalyst on a fluidized bed reactor, and adding the catalyst on a reactor C₂H₄:HCl:O₂The raw material ratio is 1: (1.8-2.0): (0.5-0.6), at 230 ℃ and under 0.32MPa, and the reaction results of different catalysts are shown in Table 2.

TABLE 1

TABLE 2

According to the data in tables 1 and 2, the spherical mesoporous alumina carrier prepared by the invention and the oxychlorination catalyst obtained by loading active components on the surface of the spherical mesoporous alumina carrier have the advantages of high specific surface area, high pore volume, regular and ordered pore size distribution and the like. The structure characteristic enables the dispersion degree of the active components to be better, the transmission of reactants to be more efficient, the load capacity of the active components to be reduced, simultaneously, the high catalytic activity can be kept, and the selectivity of ethylene and the conversion rate of hydrogen chloride in the reaction are kept at a high level.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.