CN113209958B - Zn-doped solid solution catalyst, preparation and application thereof - Google Patents
Zn-doped solid solution catalyst, preparation and application thereof Download PDFInfo
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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Abstract
The invention relates to a preparation method and application of a solid solution catalyst. The preparation method of the solid solution catalyst comprises the following specific steps: zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O, cadmium nitrate tetrahydrate (Cd (NO) 3 ) 2 ·4H 2 O) and zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O), dissolving ammonium carbonate, dripping ammonium carbonate, cooling, washing, drying 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 with the solid solution structure is directly synthesized by a high-temperature calcination method, and the catalyst can be applied to the field of preparing methanol by thermally catalyzing carbon dioxide hydrogenation.
Description
Technical Field
The invention relates to solid-solution Zn-CdZrO x Preparation of catalyst and its application. The catalyst is applied to preparing methanol by hydrogenation of carbon dioxide through thermal catalysis, shows high-efficiency and stable methanol production activity, and is expected to be applied to other fields.
Background
CO 2 The catalytic system for preparing the methanol by hydrogenation also comprises a metal oxide catalytic system besides the Cu-based and noble metal-based catalysts. Researchers Malcat [ Malcet G, lindeman A E, somorjai G A. Cobalt Particle Size Effects in the Fischer-Tropsch Synthesis and in the Hydrogenation of CO 2 Studied with Nanoparticle Model Catalysts on Silica[J].Topics in Catalysis,2014(57):500-507.]And Alayogou [ Alayogu s.CO 2 hydrogenation Studies on Co and CoPt Bimetallic Nanoparticles Under Reaction Conditions Using TEM,XPS,and NEXAFS[J].Topics in Catalysis,2014,57:500-507.]Separately investigated CoPt bimetallic catalysts, both of which are in CO 2 Hydrogenation for preparing CH 3 The conversion of carbon dioxide in OH applications is very low, only 5%, CH 4 And CO as the main products. Sharafutdinov et al [ Sharafutdinov I, abild-Pedersen F, hummelshj S, et al].Nature Chemistry,2014,6(04):320-324]Metallic compounds of Ni and Ga were investigated as catalysts and applied to CO 2 Hydrogenation for preparing CH 3 OH, the type of metal compound was found to influence the catalytic activity.
In the carbon dioxide methanolizing reaction, noble metal series (Rh, ru, pt, etc.) catalysts have excellent low-temperature catalytic activity and selectivity, but their expensive price and scarcity greatly limit their applications. Cu-based catalysts generally have better low temperature catalytic activity, but methanol selectivity is generally lower. In contrast, zr-based non-noble metal catalysts are receiving increasing attention due to their good low-temperature catalytic activity and lower cost. Therefore, the development of the Zr-based catalyst with good catalytic activity, selectivity and stability under low temperature conditions has important significance in the application of carbon dioxide methanolization, and is a research hotspot and challenge in the field.
Jijie Wang et al [ Wang J, tang C, li G, han Z, li Z, liu H, cheng F, li C.2019.High-Performance MaZrO x (Ma＝Cd,Ga)Solid-Solution Catalysts for CO 2 Hydrogenation to Methanol[J].ACS Catalysis,9(11):10253-10259.；Wang J,Li G,Li Z,Tang C,Feng Z,An H,Liu H,Liu T,Li C.2017.A highly selective and stable ZnO-ZrO 2 solid solution catalyst for CO 2 hydrogenation to methanol[J].Science Advances,3(10)]The research finds that the metal oxide solid solution catalyst CdZrO x 、ZnO-ZrO 2 In CO 2 The field of preparing methanol by catalytic hydrogenation, CO thereof 2 The conversion rate can reach 10-12.4%, the methanol selectivity can reach 80-86%, and the solid solution structure causes the synergistic effect among Cd, zn and Zr, wherein the Cd and Zn are respectively doped in ZrO as solutes 2 In the matrix. The synergistic effect in the hydrogen activation process improves the CO content of the solid solution catalyst 2 Activity and selectivity of hydrogenation to methanol. Solid solution catalyst with double active centers for developing CO with high activity and high selectivity 2 The hydrogenation catalyst opens up a new way. Therefore, cd and Zn are taken as solutes and are doped in ZrO together 2 In the matrix, the solid solution catalyst is promoted to CO by providing more active sites 2 Activity and selectivity of hydrogenation to methanol.
Disclosure of Invention
The object of the present invention is to improve the binary solid solution CdZrO x The structure of (2) is used for improving the selectivity and yield of the reaction by doping Zn element.
Technical scheme of the invention
Zn-doped solid solution Zn-CdZrO x The preparation method of the catalyst comprises the following specific steps:
(1) 0.290g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.392g cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O) and 4.192g Zr (NO) 3 ) 4 ·5H 2 Dissolving O in a 500mL three-neck flask filled with 200mL deionized water, heating to 70 ℃ by using a water bath kettle, and stirring for 30min until the solid is completely dissolved;
(2) Adding 2.342g of (NH) dissolved in the solution of the step (1) dropwise by using a separating funnel 4 ) 2 CO 3 100mL of aqueous solution; after the solution begins to generate white precipitate, continuously stirring for 2 hours at 70 ℃;
(3) Cooling the white suspension liquid obtained in the step (2), removing supernatant liquid to obtain white precipitate, washing the white precipitate with deionized water for 3-5 times to obtain a filter cake, and then putting the filter cake into a forced air drying oven to be dried for 3-5 hours at the temperature of 80-120 ℃;
(4) White ZnCO obtained after drying 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5-2 h, transferring to a muffle furnace, calcining for 2-5 h at 500 ℃ in the atmosphere of air at normal pressure, and raising the temperature at 2-10 ℃/min.
The invention has the advantages that: the preparation method has the advantages of simple process flow, mild conditions, low cost and high yield, is suitable for large-scale production, and the prepared Zn-CdZrO x A solid solution structure is presented. The catalyst can be applied to CO 2 The field of preparing methanol by thermocatalytic hydrogenation is expected to be widely applied to other fields.
Drawings
FIG. 1 Zn-CdZrO prepared in examples 1 to 4 x XRD pattern of (a).
FIG. 2 preparation of example 1Prepared Zn-CdZrO x Scanning electron microscope (TEM). Wherein a is at a magnification of 10nm and b is at a magnification of 5nm
FIG. 3 Zn-CdZrO prepared in examples 1 to 4 x Thermocatalytic CO 2 Hydrogenation methanol production activity diagram.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1:
0.290g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.392g cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O) and 4.192g Zr (NO) 3 ) 4 ·5H 2 Dissolving O in a 500mL three-neck flask containing 200mL deionized water, heating to 70 ℃ with a water bath kettle, and stirring for 30min until the solid is completely dissolved; 2.342g of (NH) dissolved therein was added dropwise via a separatory funnel 4 ) 2 CO 3 100mL of aqueous solution;
after white precipitates appear, continuously stirring for 2 hours at 70 ℃, cooling the white suspension to room temperature, removing supernatant to obtain white precipitates, washing the white precipitates with deionized water for 4 times to obtain filter cakes, and then putting the filter cakes into a forced air drying oven to dry for 4 hours at 100 ℃; white ZnCO obtained after drying 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5h, transferring to a muffle furnace, calcining for 3h at 500 ℃ in an air atmosphere at normal pressure, wherein the heating rate from room temperature to calcination is 2 ℃/min. Cooling to room temperature after calcination to obtain a solid solution catalyst 5.0% x ；
Evaluation was carried out on a FD-2000 high-pressure fixed-bed microreactor apparatus with a methanol yield of
Example 2:
0.141g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.392g cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O) and 4.192g Zr (NO) 3 ) 4 ·5H 2 Dissolving O in a 500mL three-neck flask filled with 200mL deionized water, heating to 70 ℃ by using a water bath kettle, and stirring for 30min until the solid is completely dissolved; 2.290g of (NH) dissolved therein was added dropwise via a separatory funnel 4 ) 2 CO 3 100mL of aqueous solution;
after white precipitates appear, continuously stirring for 2 hours at 70 ℃, cooling the white suspension to room temperature, removing supernatant to obtain white precipitates, washing the white precipitates with deionized water for 4 times to obtain filter cakes, and then putting the filter cakes into a forced air drying oven to dry for 4 hours at 100 ℃; white ZnCO obtained after drying 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5h, transferring to a muffle furnace, calcining at 500 ℃ for 3h in the atmosphere of air at normal pressure, wherein the temperature rising rate from room temperature to calcination is 2 ℃/min. Cooling to room temperature after calcination to obtain the solid solution catalyst 2.5% x ；
The evaluation was carried out on an FD-2000 high-pressure fixed bed microreactor apparatus with a methanol yield of 158.776
Example 3:
0.612g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.392g cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O) and 4.192g Zr (NO) 3 ) 4 ·5H 2 Dissolving O in a 500mL three-neck flask filled with 200mL deionized water, heating to 70 ℃ by using a water bath kettle, and stirring for 30min until the solid is completely dissolved; 2.45g of (NH) dissolved therein was added dropwise via a separatory funnel 4 ) 2 CO 3 100mL of aqueous solution;
after white precipitates appear, continuously stirring for 2 hours at 70 ℃, cooling the white suspension to room temperature, removing supernatant to obtain white precipitates, washing the white precipitates with deionized water for 4 times to obtain filter cakes, and then putting the filter cakes into a forced air drying oven to dry for 4 hours at 100 ℃; white ZnCO obtained after drying 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5h and then rotatingTransferring the mixture into a muffle furnace, calcining the mixture for 3h at 500 ℃ in an air atmosphere at normal pressure, and raising the temperature from room temperature to calcination at a rate of 2 ℃/min. Cooling to room temperature after calcination to obtain a solid solution catalyst 10.0% x ；
Evaluation was carried out on a FD-2000 high-pressure fixed-bed microreactor apparatus with a methanol yield of
Example 4:
0.0g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), 0.392g cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O) and 4.192g Zr (NO) 3 ) 4 ·5H 2 Dissolving O in a 500mL three-neck flask filled with 200mL deionized water, heating to 70 ℃ by using a water bath kettle, and stirring for 30min until the solid is completely dissolved; 2.25g of (NH) dissolved therein was added dropwise from a separatory funnel 4 ) 2 CO 3 100mL of aqueous solution;
after white precipitates appear, continuously stirring for 2 hours at 70 ℃, cooling the white suspension to room temperature, removing supernatant to obtain white precipitates, washing the white precipitates with deionized water for 4 times to obtain filter cakes, and then putting the filter cakes into a forced air drying oven to dry for 4 hours at 100 ℃; white ZnCO obtained after drying 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5h, transferring to a muffle furnace, calcining at 500 ℃ for 3h in the atmosphere of air at normal pressure, wherein the temperature rising rate from room temperature to calcination is 2 ℃/min. Cooling to room temperature after calcination to obtain a solid solution catalyst 0% x ；
The evaluation was carried out on an FD-2000 high-pressure fixed-bed microreactor unit with a methanol yield of 149.786
From XRD in FIG. 1, it can be seen that a cubic phase Zr-based solid solution catalyst (CdZrO) is synthesized x The expression of solid solution is that no other one can be foundPeak of component (CdO), zrO showing only cubic phase 2 Peak of (3), 5.0% of the synthesized Zn-CdZrO can be seen from the TEM of FIG. 2 x In the presence of t-ZrO 2 (011) The crystal lattices of (1), znO and CdO were not detected, indicating that ZnO was successfully doped into CdZrO x In solid solution, it is mutually confirmed by XRD.
Thermocatalytic CO 2 The reaction conditions of the hydrogenation methanol preparation reaction are as follows: 0.1g of 0.0%, 2.5%, 5.0%, 10.0% was concentrated x The solid solution catalyst was diluted with 0.4g of quartz sand, respectively, and then introduced into a stainless steel reaction tube having an inner diameter of 10mm, followed by introduction of H 2 :N 2 Volume ratio of 0.1-0.5 (here specifically 0.2) is pretreated in situ for 1-2 (here specifically 2) hours at normal pressure, after which the volume ratio H is switched directly 2 :CO 2 1-4 (specifically 4 here) under the conditions that the reaction pressure is 5.0Mpa, the flow rate of the reaction gas is 40mL/min, the optimal reaction temperature is 320 ℃, the temperature rise rate is 5 ℃/min, and after 3 hours of reaction, gas chromatography and online sampling detection are carried out;
in order to prevent condensation of reaction products, the reaction products need to be 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 ℃.
Claims (10)
1. A preparation method of a Zn-doped solid solution catalyst is characterized by comprising the following steps: zinc nitrate, cadmium nitrate and zirconium nitrate are used as raw materials, and are synthesized by a coprecipitation method to prepare Zn-CdZrO with a solid solution structure x A catalyst; the specific process is that 0.01 to 0.612g of zinc nitrate, 0.125 to 0.392g of cadmium nitrate and 4.192 to 6.691g of zirconium nitrate are added into 100 to 300mL of deionized water to be dissolved at the temperature of between 50 and 80 ℃, and 80 to 300mL of aqueous solution containing 2.25 to 2.45g of ammonium carbonate is dripped; stirring is continued after white precipitation appears, and then the precipitate is washed and dried to obtain ZnCO 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Calcining to obtain Zn-CdZrO with solid solution structure x A catalyst.
2. The process for producing a solid solution catalyst according to claim 1The method is characterized in that: zinc nitrate, cadmium nitrate and zirconium nitrate are used as raw materials, and are synthesized by a coprecipitation method to prepare Zn-CdZrO with a solid solution structure x A catalyst; the specific process is that 0.141-0.612g of zinc nitrate, 0.392g of cadmium nitrate and 4.192 of zirconium nitrate are added into 150-250mL of deionized water to be dissolved at 60-80 ℃, and then 100-200mL of aqueous solution containing 2.34g of ammonium carbonate is dripped; stirring is continued after white precipitation appears, and then the precipitate is washed and dried to obtain ZnCO 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Calcining to obtain Zn-CdZrO with solid solution structure x A catalyst.
3. The preparation method of the solid solution catalyst according to claim 1, wherein 0.3-10.0% of Zn-CdZrO is prepared x (ii) a Wherein 0.3% -10.0% represents the mass fraction of Zn element
，m Zn Represents the mass of Zn element;m CdZrOx represents CdZrO x The mass of (c); x in the solid solution represents the mole number of the content of O atom required by the mole content of metal atom under the corresponding metal valence, wherein the valence corresponding to Zn, cd and Zr elements are respectively +2 valence, +4 valence, and the valence corresponding to O is respectively-2 valence; zn-CdZrO x In (1)
，n Cd Represents the amount of a substance of Cd element;n Zr the amount of a substance representing Zr element;n Zn represents the amount of a substance of Zn element.
4. The method of claim 1, wherein: the time for continuing stirring treatment after white precipitation appears is 90-120 min; cooling the solution to 20-40 ℃, removing supernatant, and washing the precipitate with deionized water for 3-5 times in sequence at a drying temperature of 80-120 ℃; drying for 2-5 h; obtaining ZnCO 3 -CdCO 3 -Zr 2 (CO 3 ) 4 。
5. The method of claim 4, wherein:
the time for continuous stirring treatment after white precipitation appears is 100-120min; cooling the solution to 20-40 ℃, removing supernatant, and washing the precipitate with deionized water for 3-5 times in sequence at a drying temperature of 100-120 ℃; drying for 3 to 5 hours; obtaining ZnCO 3 -CdCO 3 -Zr 2 (CO 3 ) 4 。
6. The method of claim 1, wherein:
Zn-CdZrO x the preparation of (1): znCO is reacted with 3 -CdCO 3 -Zr 2 (CO 3 ) 4 Grinding for 0.5-2 h, transferring to a muffle furnace for calcining, calcining at 300-700 ℃ for 1.5-5 h in an air atmosphere, and raising the temperature from room temperature to a drying temperature to a calcining temperature at a rate of 2-10 ℃/min; cooling to 20-40 ℃ after calcining to obtain 0.3-10.0% Zn-CdZrO x A catalyst.
7. The method of claim 1, wherein:
Zn-CdZrO x the preparation of (1): the calcining temperature is 400-600 ℃, the calcining time is 2-4 h, and the heating rate from the room temperature to the drying temperature to the calcining temperature is 2-5 ℃/min.
8. A solid solution catalyst doped with Zn element prepared by the preparation method as described in any one of claims 1 to 4.
9. A Zn-CdZrO according to claim 8 x The catalyst is used as an active component and/or a carrier of the catalyst in the process of preparing methanol by carbon dioxide thermocatalytic hydrogenation.
10. The use of claim 9, wherein:
the Zn-CdZrO x The catalyst is used as an active component of the catalyst for preparing methanol by carbon dioxide thermocatalytic hydrogenation.
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| CN115845830A (en) * | 2022-08-30 | 2023-03-28 | 宁夏大学 | Preparation and application of solid solution In-ZnZrOx catalyst doped with In element |
| CN115709081B (en) * | 2022-10-14 | 2024-02-20 | 华南师范大学 | Solid solution porous microsphere, preparation method thereof and application of solid solution porous microsphere in photocatalytic hydrogen production |
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