WO2021042874A1 - Catalyseur à base de nickel pour méthanation de dioxyde de carbone, son procédé de préparation et son application - Google Patents

Catalyseur à base de nickel pour méthanation de dioxyde de carbone, son procédé de préparation et son application Download PDF

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WO2021042874A1
WO2021042874A1 PCT/CN2020/102005 CN2020102005W WO2021042874A1 WO 2021042874 A1 WO2021042874 A1 WO 2021042874A1 CN 2020102005 W CN2020102005 W CN 2020102005W WO 2021042874 A1 WO2021042874 A1 WO 2021042874A1
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based catalyst
nickel
catalyst
supported nickel
carbon dioxide
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PCT/CN2020/102005
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English (en)
Chinese (zh)
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朱明辉
韩一帆
徐晶
曹昕宇
沈亮
陈嘉成
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华东理工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a catalyst for methanation reaction, in particular to a nickel-based catalyst for carbon dioxide methanation, and a preparation method and application thereof.
  • Methanation of carbon dioxide is a strong exothermic reaction, catalyzed by transition metals, especially group VIII metals with good catalytic activity.
  • the catalysts reported in the current research mainly include metal catalysts based on ruthenium, rhodium, palladium and nickel. As precious metals, ruthenium, rhodium, and palladium are difficult to realize industrialization.
  • the nickel-based catalyst has low cost and good activity, and has a good industrialization prospect.
  • Nirium oxide is the one with better activity.
  • oxygen vacancies on the surface of nickel/cerium oxide which has good carbon dioxide adsorption capacity. According to the literature (Hiroki Muroyama et al. Journal of Catalysis 2016, 343, 178-184.), it is reported that the methane yield reaches 70%, and the selectivity is close to 100%.
  • the nickel/cerium oxide catalytic system is easy to sinter at high temperatures, and the stability needs to be improved, and the methane yield also has a large room for improvement. Therefore, there is an urgent need in the art to further improve the stability and activity of the nickel-based carbon dioxide methanation catalyst while maintaining high selectivity.
  • the purpose of the present invention is to provide a nickel-based catalyst for carbon dioxide methanation and a preparation method and application thereof in order to overcome the above-mentioned defects in the prior art.
  • the supported nickel-based catalyst used for the methanation of carbon dioxide in the present invention is a mixed oxide composed of the following components by weight:
  • the metal oxide carrier is ceria.
  • the doped metal oxide is yttrium trioxide.
  • the preparation method of the above-mentioned supported nickel-based catalyst in the present invention includes the following steps:
  • the concentration of the carbonate solution is 0.5 mol/L.
  • the carbonate solution is an ammonium carbonate solution.
  • metal salts of nickel, cerium and yttrium are all corresponding metal nitrates.
  • the reaction gas is contacted and reacted with the supported nickel-based catalyst under the conditions of a reaction temperature of 200-450°C, a reaction pressure of normal pressure, and a space velocity of 30000L/(kg ⁇ h) Methane.
  • reaction gas is a mixed gas composed of hydrogen, carbon dioxide and inert gas.
  • the supported nickel-based catalyst is activated with a reaction gas for 2 to 3 hours before the reaction, and the activation temperature is 400 to 450 hours.
  • the present invention has the following advantages:
  • the supported nickel-based catalyst synthesized by the present invention is added with doped yttrium metal.
  • the basic sites of yttrium oxide enhance the ability of carbon dioxide adsorption, so that the catalyst has a higher methanation activity than cerium monooxide at the same temperature.
  • the activity of the carrier increases the methane yield by nearly 10% compared to the single carrier, and the highest is 78%.
  • the stability of the catalyst is also higher than that when the cerium monooxide is the carrier.
  • the catalyst of the present invention is prepared by co-precipitating nickel metal salt and a precursor of cerium/yttrium metal salt.
  • the method is simple, the ratio of cerium/yttrium can be adjusted, and it can be applied to large-scale industrial production.
  • Figure 1 is an activity data diagram of each catalyst sample in the present invention.
  • Figure 2 is a TEM image of a 0.3NiO-0.3Y 2 O 3 -CeO 2 catalyst sample in the present invention
  • Figure 3 is an XRD pattern of each catalyst sample in the present invention.
  • Figure 4 is an H 2 -TPR diagram of each catalyst sample in the present invention.
  • Figure 5 is a BET diagram of each catalyst sample in the present invention.
  • the carbon dioxide methanation catalyst was prepared by the co-precipitation method using ammonium carbonate as the precipitant. By adding a certain amount of ammonium carbonate to the salt solution of nickel metal, cerium metal and yttrium metal at a certain rate, the reaction occurred and precipitated. After filtering, drying, grinding and calcining, the catalyst is obtained. By incorporating yttrium metal into the nickel-based catalyst, the activity and stability of the original nickel-based catalyst are improved.
  • step S2 Add 50 mL of 0.5 mol/L ammonium carbonate solution to the solution obtained in step S1, with a dropping rate of 1-2 mL/s;
  • step S3 After continuing to stir the mixture obtained in step S2 for 30 minutes, let it stand for 12 hours;
  • step S4 Suction filtration and washing of the mixture obtained in step S3, and the washing water volume is 300 mL;
  • step S5 Put the solid material obtained in step S4 into a vacuum oven for 12 hours, and set the temperature to 60°C;
  • step S6 Grind the solid obtained in step S5 into powder, and calcinate in a muffle furnace at 400-500° C. for 3-5 hours to obtain the final product.
  • the performance test of the catalyst in this experiment was carried out in a micro fixed-bed reactor.
  • the application process for the carbon dioxide methanation catalyst was as follows: Weigh 100mg of the catalyst, and activate it by injecting feed gas at a temperature of 450°C and atmospheric pressure at 50mL/min.
  • the catalyst performance test is carried out after 2h, and several temperature control points are set in the experiment: 200, 225, 250, 275, 300, 350, 400, 450.
  • the temperature is tested from high to low, and each temperature is kept for 80 minutes.
  • the reaction results are shown in the table. 1.
  • step S2 Add 50 mL of 0.5 mol/L ammonium carbonate solution to the solution obtained in step S1, with a dropping rate of 1-2 mL/s;
  • step S3 After continuing to stir the mixture obtained in step S2 for 30 minutes, let it stand for 12 hours;
  • step S4 Suction filtration and washing of the mixture obtained in step S3, and the washing water volume is 300 mL;
  • step S5 Put the solid material obtained in step S4 into a vacuum oven for 12 hours, and set the temperature to 60°C;
  • step S6 Grind the solid obtained in step S5 into powder, and calcinate in a muffle furnace at 400-500° C. for 3-5 hours to obtain the final product.
  • the performance test of the catalyst in this experiment was carried out in a micro fixed-bed reactor.
  • the application process for the carbon dioxide methanation catalyst was as follows: Weigh 100mg of the catalyst, and activate it by injecting feed gas at a temperature of 450°C and atmospheric pressure at 50mL/min.
  • the catalyst performance test is carried out after 2h, and several temperature control points are set in the experiment: 200, 225, 250, 275, 300, 350, 400, 450.
  • the temperature is tested from high to low, and each temperature is kept for 80 minutes.
  • the reaction results are shown in the table. 1.
  • step S2 Add 50 mL of 0.5 mol/L ammonium carbonate solution to the solution obtained in step S1, with a dropping rate of 1-2 mL/s;
  • step S3 After continuing to stir the mixture obtained in step S2 for 30 minutes, let it stand for 12 hours;
  • step S4 Suction filtration and washing of the mixture obtained in step S3, and the washing water volume is 300 mL;
  • step S5 Put the solid material obtained in step S4 into a vacuum oven for 12 hours, and set the temperature to 60°C;
  • step S6 Grind the solid obtained in step S5 into powder, and calcinate in a muffle furnace at 400-500° C. for 3-5 hours to obtain the final product.
  • the performance test of the catalyst in this experiment was carried out in a micro fixed-bed reactor.
  • the application process for the carbon dioxide methanation catalyst was as follows: Weigh 100mg of the catalyst, and activate it by injecting feed gas at a temperature of 450°C and atmospheric pressure at 50mL/min.
  • the catalyst performance test is carried out after 2h, and several temperature control points are set in the experiment: 200, 225, 250, 275, 300, 350, 400, 450.
  • the temperature is tested from high to low, and each temperature is kept for 80 minutes.
  • the reaction results are shown in the table. 1.
  • step S2 Add 50 mL of 0.5 mol/L ammonium carbonate solution to the solution obtained in step S1, with a dropping rate of 1-2 mL/s;
  • step S3 After continuing to stir the mixture obtained in step S2 for 30 minutes, let it stand for 12 hours;
  • step S4 Suction filtration and washing of the mixture obtained in step S3, and the washing water volume is 300 mL;
  • step S5 Put the solid material obtained in step S4 into a vacuum oven for 12 hours, and set the temperature to 60°C;
  • step S6 Grind the solid obtained in step S5 into powder, and calcinate in a muffle furnace at 400-500° C. for 3-5 hours to obtain the final product.
  • the performance test of the catalyst in this experiment was carried out in a micro fixed-bed reactor.
  • the application process for the carbon dioxide methanation catalyst was as follows: Weigh 100mg of the catalyst, and activate it by injecting feed gas at a temperature of 450°C and atmospheric pressure at 50mL/min.
  • the catalyst performance test is carried out after 2h, and several temperature control points are set in the experiment: 200, 225, 250, 275, 300, 350, 400, 450.
  • the temperature is tested from high to low, and each temperature is kept for 80 minutes.
  • the reaction results are shown in the table. 1.
  • step S2 Add 50 mL of 0.5 mol/L ammonium carbonate solution to the solution obtained in step S1, with a dropping rate of 1-2 mL/s;
  • step S3 After continuing to stir the mixture obtained in step S2 for 30 minutes, let it stand for 12 hours;
  • step S4 Suction filtration and washing of the mixture obtained in step S3, and the washing water volume is 300 mL;
  • step S5 Put the solid material obtained in step S4 into a vacuum oven for 12 hours, and set the temperature to 60°C;
  • step S6 Grind the solid obtained in step S5 into powder, and calcinate in a muffle furnace at 400-500° C. for 3-5 hours to obtain the final product.
  • the performance test of the catalyst in this experiment was carried out in a micro fixed-bed reactor.
  • the application process for the carbon dioxide methanation catalyst was as follows: Weigh 100mg of the catalyst, and activate it by injecting feed gas at a temperature of 450°C and atmospheric pressure at 50mL/min.
  • the catalyst performance test was carried out after 2h, and several temperature control points were set in the experiment: 200, 225, 250, 275, 300, 350, 400, 450. The temperature was tested from high to low, and each temperature was kept for 80 minutes. The reaction results are shown in the table. 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur supporté à base de nickel pour une réaction de méthanation de dioxyde de carbone. Le catalyseur supporté à base de nickel est un oxyde mixte composé des composants suivants en parties en poids : 3 Parties d'oxyde de nickel, 4-6 parties de support d'oxyde métallique et 1-3 parties d'oxyde métallique dopé. Un support modifié dopé est utilisé pour le catalyseur ; par comparaison avec la solution à l'aide d'un support unique, le rendement en méthane est fortement augmenté tout en maintenant une sélectivité élevée, en particulier dans la section à basse température (250°C), le taux d'augmentation dépasse 100%, et le rendement en méthane est jusqu'à 78%. De plus, la stabilité du catalyseur est également supérieure à celle du catalyseur avec de l'oxyde de cérium comme support, de sorte que le goulot d'étranglement d'incapacité à réaliser une activité, une sélectivité et une stabilité élevées du système catalytique existant est surmonté. Le catalyseur peut être préparé par co-précipitation ; le procédé est simple, et le rapport cérium/yttrium est réglable. La présente invention est appropriée pour une production industrielle à grande échelle.
PCT/CN2020/102005 2019-09-02 2020-07-15 Catalyseur à base de nickel pour méthanation de dioxyde de carbone, son procédé de préparation et son application WO2021042874A1 (fr)

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CN110433815A (zh) * 2019-09-02 2019-11-12 华东理工大学 一种二氧化碳甲烷化镍基催化剂及其制备方法和应用
CN111589462A (zh) * 2020-06-18 2020-08-28 南京工业大学 镍基催化剂、制备方法及用途
CN112387283A (zh) * 2020-11-28 2021-02-23 郑州大学 一种低温二氧化碳甲烷化催化剂及其制备方法

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