阅读说明：本技术 一种ZnZrOx/MoS2复合催化剂及其制备和应用 (ZnZrOx/MoS2Composite catalyst, preparation and application thereof ) 是由 马保军 田鑫 党钰莹 于 2021-08-31 设计创作，主要内容包括：本发明涉及的是一种复合催化剂的制备及其应用。该复合催化剂的制备采用如下具体步骤：将四水合钼酸铵((NH-(4))-(6)Mo-(7)O-(24)·4H-(2)O)和硫脲(CH-(4)N-(2)S)溶解,水热反应后,冷却,离心,洗涤,干燥,得到MoS-(2)。再将六水合硝酸锌(Zn(NO-(3))-(2)·6H-(2)O)和五水合硝酸锆(Zr(NO-(3))-(4)·5H-(2)O)溶解,把MoS-(2)加入其中后,浸渍蒸干,研磨,高温煅烧,获得目的产物。本发明的优点是：制备条件温和,工艺简单,价格低廉,该催化剂可应用于热催化二氧化碳加氢制甲醇领域,且甲醇产物表现出高选择性。(The invention relates to a preparation method and application of a composite catalyst. The preparation of the composite catalyst adopts the following specific steps: ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) and thiourea (CH) 4 N 2 S) dissolving, carrying out hydrothermal reaction, cooling, centrifuging, washing and drying to obtain MoS 2 . Then zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O) dissolving and MoS 2 Adding the raw materials into the mixture, dipping, evaporating to dryness, grinding, and calcining at high temperature to obtain the target product. The invention has the advantages that: the preparation condition is mild, the process is simple, the price is low, the catalyst can be applied to the field of preparing methanol by thermal catalysis carbon dioxide hydrogenation,and the methanol product exhibits high selectivity.)

1. ZnZrO_x/MoS₂The preparation method of the composite catalyst is characterized by comprising the following steps: 1) MoS is prepared from ammonium molybdate and thiourea by a hydrothermal method₂(ii) a 2) Loading zinc nitrate and zirconium nitrate on MoS by adopting an impregnation method₂The composite catalyst ZnZrO is prepared after calcination_x/MoS₂。

2. The method of claim 1, wherein: preparation to obtain ZnZrO_x/MoS₂(ii) a X represents the mole number of the corresponding O atom content required by the metal atom mole content under the corresponding metal valence, wherein the valence corresponding to Zn and Zr elements is +2 valence and +4 valence respectively, and the valence corresponding to O is-2 valence respectively; ZnZrO 2_xInn_ZnRepresents the amount of a substance of Zn element; n is_ZrRepresents the amount of a substance of Zr element; preference is given toMore preferably

3. The production method according to claim 1 or 2, characterized in that: MoS₂The preparation method comprises the following steps of adding 0.070-0.89 g (preferably 0.281-0.732 g, more preferably 0.420g) of ammonium molybdate and 0.127-1.614 g (preferably 0.510-1.328 g, more preferably 0.762g) of thiourea into 10-60 mL (preferably 20-40 mL, more preferably 30mL) of water, carrying out ultrasonic treatment for 10-60 min (preferably 20-40 min, more preferably 30min), transferring into a hydrothermal kettle, and reacting at 140-220 ℃ (preferably 160-200 ℃, more preferably 180 ℃) for 8-14 h (preferably 10-13 h, more preferably 12 h); cooling to room temperature, centrifuging, washing and drying to obtain MoS₂And (3) powder.

4. The process according to claim 1, wherein the ZnZrO is obtained_x/MoS₂Zn in the catalyst: the molar ratio of Mo is 1: 1-1: 3; preferably, Zn: the mol ratio of Mo is 1: 1.8-2: 2, more preferably Zn: the molar ratio of Mo is 1:2.

5. The production method according to claim 1 or 4, characterized in that: ZnZrO 2_x/MoS₂The specific preparation process of the catalyst comprises the steps of mixing 0.010-0.612 g (preferably 0.297g) of zinc nitrate andadding the calculated zirconium nitrate with the corresponding mass into 10-60 mL (preferably 20-40 mL, more preferably 30mL) of water, dissolving, and then adding the obtained solution according to the ratio of Zn: MoS is added into the mixture with the molar ratio of Mo being 1: 1-1: 3 (preferably 1:2)₂Powder is subjected to ultrasonic treatment, stirred, dipped and evaporated to dryness and then transferred into a muffle furnace, and ZnZrO is obtained after calcination_x/MoS₂A catalyst.

6. The method of claim 5, wherein: adding MoS₂After powder is processed, the power of ultrasonic treatment is 250-400W, the working frequency is 30-80 KHz, the stirring time is 0.5-5 h (preferably 1-2 h, more preferably 1h), the powder is moved into a water bath kettle to be soaked and evaporated to dryness, the water bath temperature is 60-90 ℃ (preferably 80-90 ℃, more preferably 90 ℃), the temperature is cooled to 20-40 ℃, the powder is ground and then transferred into a muffle furnace to be calcined, the calcining temperature is 300-700 ℃ (preferably 500-600 ℃, more preferably 550 ℃) in the atmosphere of normal pressure air, the calcining time is 2-8 h (preferably 2-5 h, more preferably 4h), and the heating rate from room temperature to the calcining temperature is 2-10 ℃/min (preferably 2-5 ℃, more preferably 3 ℃/min); cooling to 20-40 ℃ after calcining to obtain ZnZrO_x/MoS₂A catalyst.

7. ZnZrO prepared by the preparation method of any one of claims 1 to 6_x/MoS₂A catalyst.

8.ZnZrO of claim 7, and a method of producing the same_x/MoS₂The catalyst or the active component of the catalyst can be applied to the process of preparing methanol by carbon dioxide thermocatalytic hydrogenation.

9. The use of claim 8, wherein: the ZnZrO_x/MoS₂The catalyst or the active component of the catalyst can be applied to the preparation of methanol by carbon dioxide thermocatalytic hydrogenation; the reaction is carried out in a fixed bed reactor, and the conditions for synthesizing the methanol by hydrogenating the carbon dioxide are as follows: the pressure of the raw material gas is 3-6 MPa (preferably 4-5 MPa, more preferably 5MPa), the reaction temperature is 160-260 ℃ (preferably 180-220 ℃, more preferably 200 ℃), and the space velocity is 4000-30000 h^-1(preferably 12000-24000 h^-1More preferably 12000h^-1) Raw material gas n (H)₂)：n(CO₂) The volume ratio is 1 to 4 (preferably 3 to 4, more preferably 3).

Technical Field

The invention relates to ZnZrO_x/MoS₂Preparation and application of the composite catalyst. The catalyst is applied to preparing methanol by thermally catalyzing carbon dioxide hydrogenation, shows high-selectivity methanol production activity, and is expected to be applied to other fields.

Background

From the industrial revolution to the rapid and prosperous development of the world economy, the traditional energy is always boosting force for promoting the economic development, and the common coal, natural gas, oil and the like are continuously exploited to directly or indirectly supply energy and simultaneously discharge CO into the earth atmosphere₂The amount is increasing. Therefore, governments of various countries continuously make various energy-saving and emission-reducing policies, and the manufacturing industry is encouraged to use clean energy, and meanwhile, the development of new energy industry is encouraged, and more scientific researchers are attracted to increase CO₂Investigation of the Capture technique and for CO₂The transformation of (2) seeks a better path. Namely, the CO in the atmosphere is firstly treated by physical or chemical means₂The capture treatment is carried out, and then the gas is sealed or converted for utilization, thereby effectively reducing CO in the atmosphere₂The content of (b) plays a role in relieving the greenhouse effect, and further realizes the sustainable development of the human society.

Methanol is one of the most important industrial raw materials, can be used as a raw material in the organic chemical industry and can also be used as a clean high-quality fuel. These characteristics make them irreplaceable in the chemical and industrial sectors, in the fuel sector, in the plastics industry, in growth promoters. The most studied catalysts for synthesizing methanol by hydrogenating carbon dioxide are Cu-based catalysts, Cu-Zn-Al, Cu/Zn/Zr, Cu/Zn/Si, Cu/Zn/Zr-Li, Na, K, Ca, Mn and the like. In view of the present research results, the best results are Zr or Ti promoted CuZnAl catalysts (petrochemical, 2009, 38(5), 482; journal of fuel chemistry, 2011,39(12), 912). Although the Cu-based catalyst shows high efficiency in preparing methanol by hydrogenating carbon dioxide, the Cu-based catalyst has low methanol selectivity due to high activity and poor stability of RWGS. In addition, the preparation of methanol by carbon dioxide hydrogenation is an exothermic reaction, a large amount of heat can be released in the reaction process, and the Cu-based catalyst is poor in heat resistance and easy to sinter.

Comprehensively considering various factors in the process of preparing methanol by hydrogenating carbon dioxide, the invention develops ZnZrO for synthesizing methanol by hydrogenating carbon dioxide_x/MoS₂The composite catalyst can effectively inhibit reverse water gas shift reaction, thereby obtaining the selectivity of methanolTo an improvement.

Disclosure of Invention

The object of the invention is to convert ZnZrO_xSolid solution and MoS₂The catalyst is compounded (the structure of the catalyst is shown in figures 1-3), so that the selectivity and the yield of the reaction are improved.

Technical scheme of the invention

ZnZrO_x/MoS₂The preparation method of the composite catalyst comprises the following specific steps:

(1) 0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, ultrasonic treatment is carried out for 30min, and then the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining for reaction for 12h at 180 ℃.

(2) Cooling and centrifuging the suspension obtained in the step (1), washing with water and ethanol for 3 times respectively, and then drying in a forced air drying oven at 50-90 ℃ for 8-14 h; grinding to obtain MoS₂And (3) powder.

(3) 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O is prepared into 30mL aqueous solution and placed in a 100mL beaker, and stirred for 30min until the solid is completely dissolved.

(4) 0.32g of MoS was added to the solution of step (3)₂And carrying out ultrasonic treatment on the powder, stirring for 1h, transferring the powder into a water bath kettle, soaking and evaporating to dryness at the temperature of 60-90 ℃, cooling, grinding, transferring the powder into a muffle furnace for calcination, and calcining for 2-5 h at the temperature of 550 ℃ in an atmosphere of normal pressure air at the temperature rise rate of 2-10 ℃/min. Calcining to obtain ZnZrO_x/MoS₂A catalyst.

The invention has the advantages that: the preparation method has the advantages of simple process flow, mild conditions, low cost, high yield and suitability for large-scale production, and the prepared ZnZrO_x/MoS₂The catalyst can be applied to CO₂The field of preparing methanol by thermocatalytic hydrogenation is expected to be widely applied to other fields.

Compared with the existing process for preparing methanol from carbon dioxide, the catalyst has the advantage of high methanol selectivity.

Drawings

FIG. 1 XRD patterns of examples 1, 2, 3, 4, 5, 11

FIG. 2 ZnZrO of examples 1, 2, 3, 4, 5, 11_x/MoS₂Scanning Electron Microscopes (SEM) of the catalyst, the top row being from left to right the scanning electron microscopes of examples 1, 2, 3, the bottom row being from left to right the scanning electron microscopes of 4, 5, 11;

FIG. 3 ZnZrO of the elements in example 3_x/MoS₂A catalyst Mapping representation;

FIG. 4 ZnZrO of embodiment examples 1, 2, 3, 4, 5, 11_x/MoS₂An activity profile of the catalyst;

Detailed Description

The present invention is further illustrated by the following specific examples.

Example 1:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder.

0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:1₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:1ZnZrO obtained_x/MoS₂. At FD-2000 high pressureThe evaluation was carried out on a fixed bed microreactor apparatus, the carbon dioxide conversion was 2.34% and the methanol selectivity was 93.25%.

Example 2:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after ultrasonic treatment is carried out for 40min, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of 1:1.5 of Mo₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:1.5 ZnZrO based on the catalyst_x/MoS₂。

The evaluation was carried out on an FD-2000 high-pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 3.73% and a methanol selectivity of 92.18%.

Example 3:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after ultrasonic treatment is carried out for 20min, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated corresponding massZr(NO₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂The powder is put into the solution, after ultrasonic treatment for 60min, stirred for 1h, transferred into a water bath kettle, soaked at 90 ℃ and evaporated to dryness. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 7.43% and a methanol selectivity of 99.63%.

Example 4:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after ultrasonic treatment is carried out for 60min, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2.5₂The powder is put into the solution, after ultrasonic treatment for 60min, stirred for 1h, transferred into a water bath kettle, soaked at 90 ℃ and evaporated to dryness. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2.5 ZnZrO obtained_x/MoS₂。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor unit with a carbon dioxide conversion of 2.00% and a methanol selectivity of 90.71%.

Example 5:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:3₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:3 ZnZrO obtained_x/MoS₂。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 3.19% and a methanol selectivity of 96.08%.

Example 6:

0.732g of ammonium molybdate and 1.328g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂Powder inAnd (3) carrying out ultrasonic treatment on the solution for 30min, then stirring for 1h, transferring the solution into a water bath kettle, and soaking and evaporating at 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂(B)。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 5.97% and a methanol selectivity of 95.32%.

Example 7:

0.420g of ammonium molybdate and 0.782g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂(0.08)。

Evaluation was conducted on an FD-2000 high-pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 3.83% and a methanol selectivity of 89.72%.

Example 8:

weighing 0.420g of ammonium molybdate and 0.782g of thiourea to prepare 30mL of aqueous solution, placing the aqueous solution in a 100mL beaker, ultrasonically treating for 30min, quickly transferring the aqueous solution into a hydrothermal kettle with a polytetrafluoroethylene material lining, and carrying out reverse reaction at 180 DEG CAnd the time is 12 hours. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 4h at 550 ℃, wherein the heating rate is 3 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂(0.36)。

The evaluation was carried out on an FD-2000 high-pressure fixed-bed microreactor apparatus with a carbon dioxide conversion of 2.51% and a methanol selectivity of 79.96%.

Example 9:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 6h at 500 ℃,the heating rate is 8 ℃/min, and ZnZrO is obtained after grinding_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂(500)。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor unit with a carbon dioxide conversion of 6.02% and a methanol selectivity of 92.47%.

Example 10:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. 0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂O30 mL of aqueous solution was prepared and placed in a 100mL beaker and stirred until the solid was completely dissolved. According to the Zn: MoS is added into the mixture with the molar ratio of Mo being 1:2₂The powder is put into the solution, after 30min of ultrasonic treatment, stirred for 1h, transferred into a water bath kettle, soaked and evaporated to dryness at the temperature of 90 ℃. Grinding after cooling to room temperature, placing the obtained powder in a muffle furnace, calcining for 3h at 600 ℃, wherein the heating rate is 5 ℃/min, and grinding to obtain ZnZrO_x/MoS₂Catalyst, 1:2 ZnZrO obtained_x/MoS₂(600)。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 6.79% and a methanol selectivity of 94.21%.

Example 11:

0.420g of ammonium molybdate and 0.762g of thiourea are weighed to prepare 30mL of aqueous solution, the aqueous solution is placed in a 100mL beaker, after 30min of ultrasonic treatment, the aqueous solution is quickly transferred into a hydrothermal kettle with a polytetrafluoroethylene material lining, and the hydrothermal kettle reacts for 12h at 180 ℃. Cooling to room temperature, centrifuging, washing with water and ethanol for 3 times, and oven drying the precipitate at 60 deg.C. Grinding to obtain MoS₂And (3) powder. The catalyst obtained is recorded as MoS₂. The evaluation was carried out on an FD-2000 high-pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 7.15% and a methanol selectivity of 92.18%.

Example 12:

0.297g of Zn (NO)₃)₂·6H₂O and according toCalculated Zr (NO) of corresponding mass₃)₂·5H₂Dissolving O in a 500mL beaker filled with 200mL deionized water, and stirring until the solid is completely dissolved; 1.544g of (NH) dissolved therein was added dropwise via a separatory funnel₄)₂CO₃100mL of aqueous solution, the dropping speed is 3mL/min, after white precipitation appears, stirring is continued for 2 hours at 70 ℃, white suspension is cooled to room temperature, supernatant is removed, white precipitate is obtained, filter cake obtained is washed for 4 times by deionized water, then the filter cake is placed into a forced air drying oven for drying for 4 hours at 100 ℃, is cooled, is ground, is moved into a muffle furnace, and is calcined for 3 hours at 500 ℃ in the atmosphere of normal pressure air, and the heating rate is 3 ℃/min. The catalyst obtained is described as ZnZrO_x。

Evaluation was conducted on an FD-2000 high pressure fixed bed microreactor apparatus with a carbon dioxide conversion of 10.24% and a methanol selectivity of 91.65%.

The above examples thermocatalytic CO₂The reaction conditions of the hydrogenation methanol preparation reaction are as follows: 0.2g of ZnZrO was added_x/MoS₂The catalyst was diluted with 0.2g of quartz sand, added to a stainless steel reaction tube having an inner diameter of 10mm, and purified H was added₂Pretreating in situ for 2-3 (specifically 3) hours at normal pressure, and then directly switching volume ratio H₂:CO₂Reacting raw material gas of 1: 1-4: 1 (specifically 3:1), wherein the reaction pressure is 5.0Mpa, the flow rate of the reaction gas is 40mL/min, the optimal reaction temperature is 200 ℃, the temperature rise rate is 5 ℃/min, and after reacting for 3 hours, performing gas chromatography and online sampling detection (the catalyst activity is shown in figure 4);

in order to prevent condensation of reaction products, the reaction products are heated by a glass fiber electric heating tape and then sent to a gas chromatography for on-line detection, and a KSW resistance furnace temperature controller is used for heating, wherein the heating temperature is 150 ℃.