Preparation method and application of catalyst for selectively producing ethanethiol

Abstract

The invention provides a preparation method and application of a catalyst for selective production of ethanethiol. The catalyst comprises an active component, an auxiliary agent and a molded alumina carrier, the active component comprises the following components in percentage by mass: 5-10% of VIII group transition metal oxide and 15-20% of VIB group metal oxide, and the auxiliaries comprise 0.5-4% of alkali metal, 1-3% of alkaline earth metal oxide, 0.6-2% of cerium oxide and 1-4% of phosphorus pentoxide. A bifunctional catalyst with moderate Lewis acid-base sites is constructed by compounding a multi-component aid and an active component, and the catalyst shows excellent catalytic activity that the ethylene conversion per pass is greater than or equal to 98%, the ethanethiol selectivity is about-95% and the ethanethiol yield is-90% under the reaction conditions that the hydrogen sulfide / ethylene feeding mass ratio is 3-5, the temperature is 180-210 DEG C, the pressure is 0.5-1.0 MPa and the volume space velocity is 200-300 h <-1 >. And the catalyst can stably run for 1250 hours or more.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a catalyst for selectively producing ethanethiol, and belongs to the technical field of catalyst preparation and application. Background Art

[0002] Ethanethiol is a key chemical intermediate and is widely used in the production of organophosphorus pesticides (such as isopropylphosphorus, phorate, disulfoton, methyl demeton, etc.) and broad-spectrum antibacterial agent 401, etc. In addition, it can also be used to prepare 2,2-bis(ethylsulfonyl)propane (sulfonal) and other hypnotic drugs. In addition, the odor of ethanethiol makes it usable as a warning agent for natural gas and petroleum gas, an odorant for reagents, etc. The production methods of ethanethiol include ethyl sulfate method, thiourea method, ethanol method, chloroethane method, ethylene sulfidation method, etc. At present, the chloroethane method is mainly used in China. This method has high raw material cost, and the atomic utilization rate is only about 51.53%. It is easy to generate a large amount of waste salt sodium chloride and waste water. Moreover, after the reaction, it is necessary to neutralize the unreacted sodium hydrosulfide with acid, causing serious equipment corrosion. Synthesizing ethanethiol by gas-phase catalytic reaction with ethanol as the raw material under high temperature and normal pressure at 360-380 °C is a new process route. Although this process is convenient for continuous production, there are problems such as poor selectivity, many by-products, complex products, high reaction temperature, and high energy consumption (CN118047702A). The atomic utilization rate of the process route for synthesizing ethanethiol by ethylene sulfidation method reaches 100%, and the by-product of this reaction is only diethyl sulfide. This reaction is carried out under the action of a catalyst, and the content of ethanethiol in the product reaches more than 90% without refining and can be directly used for synthesizing pesticides. Therefore, it is a very green and efficient production route. At present, this route is adopted for the production of ethanethiol abroad, such as Phillips in the United States and Arkema in France (CN117567330A, CN1307130C, CN1701053A). However, the reported Lewis acid catalysts, molecular sieve catalysts, ion exchange resins, and supported alumina-based catalysts for this reaction face problems such as poor selectivity, low yield, and short life due to carbon deposition or sulfur deposition. Therefore, the development of highly selective and highly stable catalysts is the key to stably obtaining high-yield ethanethiol by this process route. Summary of the Invention

[0003] In view of this, in response to the above problems, the present invention provides a preparation method and application of a catalyst for selectively producing ethanethiol. A bifunctional catalyst with moderately strong Lewis acid-base sites is constructed by using multi-component composite metal oxides and non-metal oxides. Through the synergistic effect of the Lewis acid-base sites, the activity and selectivity of ethylene sulfidation are greatly improved. At the same time, the moderately strong Lewis acid-base sites avoid the strong adsorption of ethylene and hydrogen sulfide, thereby slowing down the trend of the catalyst gradually deactivating due to carbon deposition or sulfur deposition.

[0004] A catalyst for the selective production of ethanethiol, wherein the catalyst uses shaped alumina balls as a carrier, Group VIII and Group VIB metal oxides as active components, and oxides of alkali metals, alkaline earth metals, lanthanide metals and non-metals as promoters; among them, the Group VIB metal oxide is 5-20%, the content of Group VIII transition metal oxide is 1-10%, the lanthanide metal oxide is 0.5-4%, the mass percentage of the alkali metal is 0.5-10%, the alkaline earth metal oxide is 0.2-5%, and the content of non-metal phosphorus pentoxide in the metal oxide is 1-4%.

[0005] The Group VIB metal oxide is one or two of MoO 3 、WO 3 , and the corresponding metal salt precursors are ammonium molybdate and ammonium metatungstate.

[0006] In some preferred cases, the metal salt precursor is (NH 4 ) 6 Mo 7 O 24 、H 28 N 6 O 41 W 12 .

[0007] The alkali metal is one or more of Li, Na, K, Cs, and the alkali metal precursor is one or more of carbonate, bicarbonate, acetate.

[0008] In some preferred cases, the alkali metal precursor is Li 2 CO 3 、Na 2 CO 3 、NaHCO 3 、CH 3 COONa、K 2 CO 3 、CH 3 COOK、KHCO 3 、Cs 2 CO 3 or one or more of them.

[0009] The alkaline earth metal oxide is one of MgO or ZnO, and the alkaline earth metal precursor is one or more of sulfate, nitrate, halide salt.

[0010] In some preferred cases, the alkaline earth metal precursor is MgSO 4 、Mg(NO 3 ) 2 、Zn(NO 3 ) 2 、ZnCl 2 or one of them.

[0011] The Group VIII transition metal oxide is Fe 2 O 3 , CoO, NiO, or one or more thereof, and the corresponding metal salt precursor is one or more of a sulfate, a nitrate, and a halide salt.

[0012] In some preferred cases, the metal salt precursor is Fe(NO 3 ) 3 , Co(NO 3 ) 2 , Ni(NO 3 ) 2 .

[0013] The lanthanide metal oxide is CeO 2 , and the corresponding metal salt precursor is one of a nitrate and a halide salt.

[0014] In some preferred cases, the metal salt precursor is Ce(NO 3 ) 3 .

[0015] A method for preparing a catalyst for selectively producing ethanethiol, comprising the following steps: 1. Sequentially dissolve the Group VIB metal precursor, the Group VIII metal precursor, and ammonium dihydrogen phosphate in water to form a uniformly dispersed impregnation solution A. Add the shaped alumina balls to the impregnation solution A by the equal-volume impregnation method, impregnate at room temperature for 2 - 6 h, then dry overnight, and then calcine at 400 - 650 °C for 3 - 12 h to obtain catalyst A.

[0016] 2. Disperse the raw materials of the alkaline earth metal oxide and the lanthanide metal oxide in water to form a clear and transparent mixed solution B. Then add catalyst A to the impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 - 5 h, then dry overnight, and then calcine at 400 - 600 °C for 2 - 5 h to obtain catalyst B; 3. Disperse the alkali metal precursor in water to form an impregnation solution C, then add catalyst B to the impregnation solution C by the equal-volume impregnation method, impregnate at room temperature for 4 h, then dry overnight, and calcine at 450 - 550 °C for 2 - 5 h to obtain the final multi-component supported catalyst.

[0017] In step 1, the addition amount of ammonium dihydrogen phosphate accounts for 1.6 - 6.5% of the total proportion.

[0018] In step 1, the Group VIII transition metal oxide is Fe 2 O 3, one or more of CoO and NiO, accounting for 1-10% of the catalyst mass fraction, preferably 5-10%, and the corresponding metal salt precursor is Fe(NO 3 ) 3 , Co(NO 3 ) 2 , Ni(NO 3 ) 2 .

[0019] In the step 1, the Group VIB metal oxide is one or two of MoO 3 , WO 3 , accounting for 5-20% of the catalyst mass fraction, preferably 15-20%, and the corresponding metal salt precursor is (NH 4 ) 6 Mo 7 O 24 , H 28 N 6 O 41 W 12 .

[0020] In the step 2, the alkaline earth metal oxide is one of MgO and ZnO, accounting for 0.2-5% of the catalyst mass fraction, preferably 1-3%, and the alkaline earth metal precursor is MgSO 4 , Mg(NO 3 ) 2 , Zn(NO 3 ) 2 , ZnCl 2 one of them.

[0021] In the step 2, the lanthanide metal oxide is CeO 2 , accounting for 0.5-4% of the catalyst mass fraction, preferably 0.6-2%, and the corresponding metal salt precursor is Ce(NO 3 ) 3 .

[0022] In the step 3, the alkali metal is one or more of Li, Na, K, and Cs, accounting for 0.5-10% of the catalyst mass fraction, preferably 0.5-4%, and the alkali metal precursor is Li 2 CO 3 , Na 2 CO 3 , NaHCO 3 , CH 3 COONa, K 2 CO 3 , KHCO 3 , CH 3 COOK, Cs 2 CO 3One or more of those, preferably Li 2 CO 3 and Na 2 CO 3 。

[0023] The bulk specific gravity of the high-performance ethanethiol synthesis catalyst prepared by the above method is 0.70 - 0.90 g / ml, the specific surface area ≥ 150 m 2 / g, the strength ≥ 100 N / grain, and the pore volume is 0.3 - 0.5 ml / g. In the ethanethiol synthesis method, a mixed gas of ethylene and hydrogen sulfide is used as the raw material, the mass ratio of hydrogen sulfide / ethylene feed is 3 - 5, and an experiment on the addition of ethylene to produce ethanethiol is carried out at 180 - 210 °C and a pressure of 0.5 - 1.0 MPa. The volume space velocity of the bed layer is 200 - 300 h -1 , the single-pass conversion rate of ethylene ≥ 98%, the selectivity of ethanethiol is about ~95%, and the yield of ethanethiol is ~90%.

[0024] Advantages and technical effects of the method of the present invention: The present invention prepares a multi-component composite catalyst. Compared with the traditional single-component or two-component supported alumina catalyst, this catalyst uses alkali metals, alkaline earth metals, lanthanide metals, and non-metal phosphorus as promoters, and transition metal oxides of Group VIB and VIII as active components to construct Lewis acid sites that are beneficial to the moderate adsorption of olefins and Lewis base sites that are beneficial to the adsorption of hydrogen sulfide. Through the synergistic effect of the Lewis acid-base sites on the surface of the composite catalyst, the ethylene conversion rate, the selectivity of ethanethiol, and the stability of the catalyst are improved. By adopting the technical solution of the present application, the single-pass conversion rate of ethylene ≥ 98%, the selectivity of ethanethiol is about ~95%, and the yield of ethanethiol is ~90% can be achieved. Description of the Drawings

[0025] Figure 1 is the stability test of the LiMgCeCoWP / Al 2 O 3 catalyst in Example 1 of the present invention. Detailed Embodiments

[0026] In order to more clearly elaborate the purpose, technical solution and corresponding advantages of the present invention, the present invention will provide a series of catalyst preparation examples and application examples of synthesizing ethanethiol by ethylene sulfidation method to detail the specific operation process and actual application effect of the present invention, so as to verify the effectiveness and practicability of the present invention.

[0027] Example 1: Preparation method of LiMgCeCoWP / Al 2 O 3 catalyst (1) 15.4 g of ammonium metatungstate, 23.3 g of cobalt nitrate hexahydrate, and 1.9 g of ammonium dihydrogen phosphate were successively dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0028] (2) 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate were dispersed in water to form a clear and transparent mixed solution B. Then, catalyst A was added to the impregnation solution B by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 600 °C for 3 h to obtain catalyst B; (3) 6.4 g of lithium carbonate precursor was dispersed in water to form an impregnation solution C. Then, catalyst B was added to the impregnation solution C by the equal-volume impregnation method, impregnated at room temperature for 4 h, dried overnight, and calcined at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0029] Example 2: LiMgCeCoMoP / Al 2 O 3 Preparation method of catalyst (1) 22.1 of ammonium molybdate tetrahydrate, 23.3 g of cobalt nitrate hexahydrate, and 1.9 g of ammonium dihydrogen phosphate were successively dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0030] (2) 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate were dispersed in water to form a clear and transparent mixed solution B. Then, catalyst A was added to the impregnation solution B by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 600 °C for 3 h to obtain catalyst B; (3) 6.4 g of lithium carbonate precursor was dispersed in water to form an impregnation solution C. Then, catalyst B was added to the impregnation solution C by the equal-volume impregnation method, impregnated at room temperature for 4 h, dried overnight, and calcined at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0031] Example 3: NaMgCeCoWP / Al 2 O 3 Preparation method of catalyst (1) 15.4 g of ammonium metatungstate, 23.3 g of cobalt nitrate hexahydrate, and 1.9 g of ammonium dihydrogen phosphate were successively dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0032] (2) 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate were dispersed in water to form a clear and transparent mixed solution B. Then, catalyst A was added to the impregnation solution B by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 600 °C for 3 h to obtain catalyst B; (3) 2.8 g of sodium carbonate precursor was dispersed in water to form an impregnation solution C. Then, catalyst B was added to the impregnation solution C by the equal-volume impregnation method, impregnated at room temperature for 4 h, dried overnight, and calcined at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0033] Comparative Example 1: LiMgCeCoW / Al 2 O 3 Preparation method of catalyst (1) 15.4 g of ammonium metatungstate and 23.3 g of cobalt nitrate hexahydrate were successively dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0034] (2) 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate were dispersed in water to form a clear and transparent mixed solution B. Then, catalyst A was added to the impregnation solution B by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 600 °C for 3 h to obtain catalyst B; (3) 6.4 g of lithium carbonate precursor was dispersed in water to form an impregnation solution C. Then, catalyst B was added to the impregnation solution C by the equal-volume impregnation method, impregnated at room temperature for 4 h, dried overnight, and calcined at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0035] Comparative Example 2: LiMgCeCoP / Al 2 O 3 Preparation method of catalyst (1) 23.3 g of cobalt nitrate hexahydrate and 1.9 g of ammonium dihydrogen phosphate were dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0036] (2) Disperse 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate in water to form a clear and transparent mixed solution B. Then, add catalyst A to the impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 600 °C for 3 h to obtain catalyst B; (3) Disperse 6.4 g of lithium carbonate precursor in water to form an impregnation solution C. Then, add catalyst B to the impregnation solution C by the equal-volume impregnation method, impregnate at room temperature for 4 h, dry overnight, and calcine at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0037] Comparative Example 3: LiMgCeWP / Al 2 O 3 Preparation method of catalyst (1) Dissolve 15.4 g of ammonium metatungstate and 1.9 g of ammonium dihydrogen phosphate in water in sequence to form a uniformly dispersed impregnation solution A. Add 120 g of shaped alumina balls to the impregnation solution A by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 650 °C for 3 h to obtain catalyst A.

[0038] (2) Disperse 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate in water to form a clear and transparent mixed solution B. Then, add catalyst A to the impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 600 °C for 3 h to obtain catalyst B; (3) Disperse 6.4 g of lithium carbonate precursor in water to form an impregnation solution C. Then, add catalyst B to the impregnation solution C by the equal-volume impregnation method, impregnate at room temperature for 4 h, dry overnight, and calcine at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0039] Comparative Example 4: LiCeCoWP / Al 2 O 3 Preparation method of catalyst (1) Dissolve 15.4 g of ammonium metatungstate, 23.3 g of cobalt nitrate hexahydrate and 1.9 g of ammonium dihydrogen phosphate in water to form a uniformly dispersed impregnation solution A. Add 120 g of shaped alumina balls to the impregnation solution A by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 650 °C for 3 h to obtain catalyst A.

[0040] (2) Disperse 3.0 g of cerium nitrate hexahydrate in water to form a clear and transparent mixed solution B. Then, add catalyst A to the impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 600 °C for 3 h to obtain catalyst B; (3) Disperse 6.4 g of lithium carbonate precursor in water to form impregnation solution C. Then, add catalyst B to impregnation solution C by the equal-volume impregnation method, impregnate at room temperature for 4 h, dry overnight, and calcine at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0041] Comparative Example 5: LiMgCoWP / Al 2 O 3 Preparation method of catalyst (1) Dissolve 15.4 g of ammonium metatungstate, 23.3 g of cobalt nitrate hexahydrate, and 1.9 g of ammonium dihydrogen phosphate in water to form a uniformly dispersed impregnation solution A. Add 120 g of shaped alumina balls to impregnation solution A by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 650 °C for 3 h to obtain catalyst A.

[0042] (2) Disperse 7.6 g of magnesium nitrate hexahydrate in water to form a clear and transparent mixed solution B. Then, add catalyst A to impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 600 °C for 3 h to obtain catalyst B; (3) Disperse 6.4 g of lithium carbonate precursor in water to form impregnation solution C. Then, add catalyst B to impregnation solution C by the equal-volume impregnation method, impregnate at room temperature for 4 h, dry overnight, and calcine at 500 °C for 3 h to obtain the final multi-component supported catalyst.

[0043] Comparative Example 6: MgCeCoWP / Al 2 O 3 Preparation method of catalyst (1) Dissolve 15.4 g of ammonium metatungstate, 23.3 g of cobalt nitrate hexahydrate, and 1.9 g of ammonium dihydrogen phosphate in water to form a uniformly dispersed impregnation solution A. Add 120 g of shaped alumina balls to impregnation solution A by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 650 °C for 3 h to obtain catalyst A.

[0044] (2) Disperse 7.6 g of magnesium nitrate hexahydrate and 3.0 g of cerium nitrate hexahydrate in water to form a clear and transparent mixed solution B. Then, add catalyst A to impregnation solution B by the equal-volume impregnation method, impregnate at room temperature for 2 h, dry overnight, and then calcine at 600 °C for 3 h to obtain catalyst B.

[0045] Comparative Example 7: CoW / Al 2 O 3 Preparation method of catalyst 15.4 g of ammonium metatungstate and 23.3 g of cobalt nitrate hexahydrate were dissolved in water to form a uniformly dispersed impregnation solution A. 120 g of shaped alumina balls were added to the impregnation solution A by the equal-volume impregnation method, impregnated at room temperature for 2 h, dried overnight, and then calcined at 650 °C for 3 h to obtain catalyst A.

[0046] Application Examples 1 - 10 The catalysts prepared in Examples 1 - 3 and Comparative Examples 1 - 7 were respectively evaluated for the performance of the addition reaction of ethylene and hydrogen sulfide to produce ethanethiol, and Application Examples 1 - 10 were obtained. The specific reaction conditions were as follows: 150 ml of the prepared multi-component supported catalyst was filled into a fixed-bed reactor. Using ethylene and hydrogen sulfide as raw materials, at a hydrogen sulfide / ethylene feed mass ratio of 3, a temperature of 190 °C, a pressure of 0.8 MPa, and a reaction space velocity of 250 h -1 an experiment on the performance evaluation of the addition reaction of ethylene to produce ethanethiol was carried out. The reaction products were on-line detected by a gas chromatography dual-channel TCD.

[0047] Application Example 11 The LiMgCeCoMoP / Al prepared in Example 1 2 O 3 catalyst was subjected to a stability test under the reaction conditions of a hydrogen sulfide / ethylene feed mass ratio of 3, a temperature of 190 °C, a pressure of 0.8 MPa, and a reaction space velocity of 250 h -1 . The results were as Figure 1 shown. The catalyst still maintained an ethylene conversion rate of >98% and an ethanethiol yield of over 87% after running for 1250 h, showing excellent stability.

[0048] Table 1. Comparison of the ethylene sulfide addition performance of a series of multi-component alumina-supported catalysts.

[0049]

[0050] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A catalyst for selectively producing ethanethiol, characterized in that, The catalyst uses formed alumina balls as carriers, group VIII and group VIB transition metal oxides as active components, and alkali metal, alkaline earth metal, lanthanide metal and non-metal oxides as additives; wherein the content of group VIII transition metal oxides is 1-10%, the content of group VIB metal oxides is 5-20%, the mass percentage of alkali metals is 0.5-10%, the mass percentage of alkaline earth metal oxides is 0.2-5%, the mass percentage of lanthanide metal oxides is 0.5-4%, and the content of non-metallic phosphorus pentoxide is 1-4%.

2. The selective production of ethanethiol catalyst according to claim 1, characterized in that The Group VIII transition metal oxide is one or more of Fe2O3, CoO, and NiO, and the corresponding metal salt precursor is one or more of sulfate, nitrate, and halide.

3. The selective production of ethanethiol catalyst as claimed in claim 1, characterized in that The VIB group metal oxide is one or two of MoO3 and WO3, and the corresponding metal salt precursor is ammonium molybdate and ammonium metatungstate.

4. The selective production of ethanethiol catalyst as claimed in claim 1, characterized in that The alkali metal is one or more of Li, Na, K, and Cs, and its alkali metal precursor is one or more of carbonate, bicarbonate, and acetate.

5. The selective production of ethanethiol catalyst according to claim 1, characterized in that The alkaline earth metal oxide is one of MgO and ZnO, and the alkaline earth metal precursor is one or more of sulfate, nitrate and halide.

6. The selective production of ethanethiol catalyst according to claim 1, characterized in that The lanthanide metal oxide is CeO2, and the corresponding metal salt precursor is one of nitrate and halide.

7. The method for preparing a catalyst for selectively producing ethanethiol according to any one of claims 1 to 6, characterized in that: The preparation process is: 1) Dissolving a Group VIB metal precursor, a Group VIII metal precursor and ammonium dihydrogen phosphate in water in sequence to form a uniformly dispersed impregnation solution A, adding the formed alumina balls into the impregnation solution A by an equal volume impregnation method, impregnating at room temperature for 2-6 hours and then drying overnight, and then calcining at 400-650 °C for 3-12 hours to obtain a catalyst A; 2) The raw materials of alkaline earth metal oxide and lanthanide metal oxide are dispersed in water to form a clear and transparent mixed solution B, and then the catalyst A is added to the impregnation solution B by an equal volume impregnation method, impregnated at room temperature for 2 to 5 hours, dried overnight, and then calcined at 400 to 600 ° C for 2 to 5 hours to obtain the catalyst B; 3) The alkali metal precursor is dispersed in water to form an impregnation solution C, and then the catalyst B is added to the impregnation solution C by an equal volume impregnation method. After impregnation at room temperature for 4 hours, it is dried overnight and calcined at 450-550 °C for 2-5 hours to obtain the final multi-component supported catalyst.

8. The method for preparing a catalyst for selectively producing ethanethiol according to claim 7, characterized in that: The prepared multi-component supported catalyst has a bulk density of 0.70-0.90 g / ml and a specific surface area of ​​140 m 2 / g, strength ≥100N / particle, pore volume 0.3~0.5 ml / g.

9. Use of the selective ethanethiol production catalyst according to any one of claims 1 to 6 or the selective ethanethiol production catalyst prepared by the method according to claim 7 or 8 in catalyzing ethylene and hydrogen sulfide to prepare ethanethiol.

10. The use according to claim 9, characterized in that: The catalyst uses ethylene and hydrogen sulfide as raw materials. The prepared multi-component supported catalyst is filled in a fixed bed reactor, and ethylene addition is carried out to prepare ethyl mercaptan at a hydrogen sulfide / ethylene feed mass ratio of 3-5, 180-210°C, and a pressure of 0.5-1.0 MPa.

Images