WO2024066032A1 - Procédé de préparation d'un catalyseur hopcalite modifié et son utilisation - Google Patents

Procédé de préparation d'un catalyseur hopcalite modifié et son utilisation Download PDF

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Publication number
WO2024066032A1
WO2024066032A1 PCT/CN2022/136499 CN2022136499W WO2024066032A1 WO 2024066032 A1 WO2024066032 A1 WO 2024066032A1 CN 2022136499 W CN2022136499 W CN 2022136499W WO 2024066032 A1 WO2024066032 A1 WO 2024066032A1
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hopcalite catalyst
catalyst
preparing
source
modified
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PCT/CN2022/136499
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English (en)
Chinese (zh)
Inventor
董浩
赵少丹
王文幼
张振国
董一涛
罗圆
封超
许龙龙
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西安向阳航天材料股份有限公司
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Publication of WO2024066032A1 publication Critical patent/WO2024066032A1/fr

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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
    • B01J23/005—Spinels
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to the technical field of catalysts for catalytic combustion of CO.
  • the catalysts that are maturely used in CO catalytic combustion are mainly precious metal catalysts.
  • the high cost has greatly limited the market application of precious metal catalysts. Therefore, the development of non-precious metal catalysts with high and low temperature activity, high stability and low cost will greatly promote the market application of catalytic combustion.
  • hopcalite catalysts with Cu, Mn oxides and their composite oxides as main components have shown high reactivity in catalytic combustion activity studies.
  • Hopcalite catalysts with MnO 2 and CuO as main components are widely used in submarine closed compartments. They can catalyze CO to CO 2 at high temperature in a 320°C burner environment. The reaction has the advantages of no secondary toxic pollutants (Christopher et al. Applied Catalysis B: Environmental, 2017, (203) 533-540).
  • hopcalite catalysts are composed of CuMn 2 O 4 spinel formed by Cu and Mn, which makes most of the Cu and Mn elements mainly exist in the catalyst in the form of carriers, while only a small amount of Cu 2+ and Mn 4+ can be dispersed and freed on the catalyst surface to form catalytic reaction active centers, making it difficult for hopcalite catalysts to obtain good low-temperature catalytic activity.
  • the object of the present invention is to provide a modified hopcalite catalyst, wherein the doping of Al forms a new spinel structure with Cu and Mn, thereby playing the role of a carrier, so that more Cu 2+ and Mn 4+ are dispersed on the catalyst surface.
  • the structure is stable, the low-temperature catalytic activity is good, and the catalytic stability is high.
  • the object of the present invention is also to provide a method for preparing the above catalyst, which has a simple process and high product stability.
  • the present invention also aims to provide an application method of the catalyst.
  • a modified hopcalite catalyst comprises the following components: a composite oxide consisting of CuAl 2 O 4 , MnAl 2 O 4 and oxides of Cu and Mn.
  • the oxide of Cu and Mn is CuMnO 2 .
  • the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
  • the molar ratio of the Cu element, the Mn element and the Al element is 5:1:0.2-3, and more preferably 5:1:0.5-1.
  • the present invention provides the following technical solutions:
  • the preparation method of the catalyst comprises the following steps: co-precipitating a mixed solution containing Cu ions, Mn ions and Al ions, and calcining the obtained precipitate.
  • the mixed solution is an acid solution containing a Cu compound, a Mn compound and an Al compound.
  • the acid solution is a nitric acid solution.
  • the calcination temperature is 300-500°C.
  • the calcination time is 6 to 10 hours.
  • the coprecipitation is carried out under alkaline conditions.
  • the coprecipitation uses an alkali as a precipitant, and the alkali is selected from one or more of sodium hydroxide, sodium carbonate and ammonia water.
  • the concentration of the base is 0.3 to 3 mol ⁇ L -1 .
  • the concentration of the base is 1.5 to 2.5 mol ⁇ L -1 .
  • the coprecipitation temperature is 10 to 30 °C.
  • the coprecipitation temperature is 15-20°C.
  • the mixed solution is allowed to stand for 10 to 20 hours after the coprecipitation.
  • the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
  • the molar ratio of the Cu element, the Mn element and the Al element is 5:1:0.5-1.
  • the total concentration of metal ions in the mixed solution is 0.5 to 1.5 mol ⁇ L -1 .
  • the Cu compound is selected from copper nitrate (Cu(NO 3 ) 2 ⁇ 3H 2 O) and/or copper sulfate (CuSO 4 ).
  • the Mn compound is selected from manganese nitrate (MnN 2 O 6 ⁇ 4H 2 O) and/or manganese nitrate solution (Mn(NO 3 ) 2 ).
  • the Al compound is selected from aluminum nitrate (Al(NO 3 ) 3 ⁇ 9H 2 O).
  • the preparation of the mixed solution includes: dissolving the copper source, the manganese source, and the aluminum source in distilled water in sequence to obtain the mixed solution.
  • the present invention provides the following technical solutions:
  • the catalyst or the catalyst prepared according to the preparation method is applied to CO catalytic combustion.
  • the particle size of the catalyst is 20-60 mesh.
  • the CO low temperature oxidation temperature is 20°C.
  • the present invention obtains a novel hopcalite catalyst for catalytic combustion of CO;
  • the present invention further doped Al 2 O 3 in the existing hopcalite catalyst, which not only improved the dispersion of the active center components Cu 2+ and Mn 4+ , but also the doping effect of metal ions further promoted the bonding strength between CO and Cu and Mn, so that the low-temperature activity and catalytic efficiency of the catalyst were significantly improved;
  • the catalyst of the present invention has better low-temperature activity in the CO catalytic combustion reaction than the traditional hopcalite catalyst, and can achieve 100% conversion of CO at room temperature of 20°C;
  • FIG. 1 is an XRD spectrum of Example 5
  • FIG. 2 is a comparison chart of H2-TPR of Example 5 and commercial Hojalat catalyst.
  • the catalyst used in the following examples was obtained by the following preparation process:
  • the pH value of the reaction solution is adjusted by adjusting the dripping rate of the two.
  • stop adding the NaOH precipitant immediately, continue stirring at room temperature for 2h, and let it stand for aging for 15h.
  • the activity of CO catalytic combustion reaction was investigated on commercial hopcalite catalyst.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced at a rate of 30 mL min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15 °C, and the CO catalytic combustion reaction was carried out. After the temperature stabilized, the data were collected 15 minutes later, and the TCD detector was used for online analysis on the SC-2000 gas chromatograph.
  • the formula for evaluating the CO conversion rate of the reactant is as follows:
  • the sampling at this temperature is terminated, and the average conversion rate of three samplings is taken as the conversion rate at this temperature. Then the temperature is increased by 5°C/time until the CO conversion rate reaches 100% and the reaction is terminated.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
  • a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
  • the commercial Hojalat catalyst and the Cu-Mn-Al composite oxide prepared with the molar ratio of Cu:Mn:Al of 5:1:0.2, 5:1:0.4, 5:1:0.6, 5:1:0.8 and 5:1:1 were mainly investigated.
  • the catalyst in Example 5 with the best low temperature activity was characterized by X-ray diffraction, and the XRD spectrum shown in Figure 1 was obtained.
  • the main crystal form in the Cu-Mn-Al catalyst is a spinel structure formed by the combination of Cu, Mn and Al elements, and a part of CuMnO 2 composite oxide was observed, which indicates that in the newly generated Cu-Mn-Al composite oxide catalyst after the addition of Al element, Al as a carrier makes the CuMn 2 O 4 spinel structure replaced by CuAl 2 O 4 and MnAl 2 O 4 , which increases the dispersion of Cu and Mn and thus obtains better catalytic activity.
  • the results of H 2 -TPR also verify this rule.
  • the catalyst in Example 5 and the commercial hopcalite catalyst were characterized by H 2 programmed temperature reduction, and the H 2 -TPR comparison spectrum shown in Figure 2 was obtained.
  • Al doping makes the Cu-Mn catalyst easier to reduce, which further proves the increase in the dispersion of Cu 2+ and Mn 2+ in the catalyst.
  • Al doping effectively reduces the interaction between the active components and the carrier, so that the dispersion of the active components free Cu 2+ and Mn 4+ on the catalyst surface is increased, the low-temperature reducibility of the catalyst is enhanced, and thus the reaction activity of catalytic combustion is improved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
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  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un catalyseur hopcalite modifié, son procédé de préparation et son utilisation. Le procédé de préparation du catalyseur hopcalite modifié comprend : le mélange de solutions contenant une source de cuivre, une source de manganèse et une source d'aluminium pour obtenir une solution mixte; la co-précipitation de la solution mélangée dans une condition alcaline pour obtenir un précipité; et la torréfaction du précipité obtenu pour obtenir finalement un catalyseur hopcalite modifié. Selon le catalyseur hopcalite modifié fourni par la présente invention, par dopage Al, Al, Cu et Mn forment une nouvelle structure de spinelle qui fonctionne comme un support, de telle sorte qu'une quantité supérieure de Cu2 + et de Mn4 + est dispersée sur la surface du catalyseur. Le catalyseur a une structure stable, une bonne activité catalytique à basse température et une stabilité catalytique élevée. Le procédé de préparation selon la présente invention présente un procédé simple et une stabilité de produit élevée.
PCT/CN2022/136499 2022-09-27 2022-12-05 Procédé de préparation d'un catalyseur hopcalite modifié et son utilisation WO2024066032A1 (fr)

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CN202211177646.8 2022-09-27
CN202211177646.8A CN115445634A (zh) 2022-09-27 2022-09-27 改性霍加拉特催化剂及其制备方法、应用

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109621967A (zh) * 2018-12-26 2019-04-16 西安向阳航天材料股份有限公司 一种铜系低温变换催化剂的制备方法
WO2019204127A1 (fr) * 2018-04-20 2019-10-24 Aether Catalyst Solutions, Inc. Catalyseur d'oxydes métalliques mixtes à base de cuivre-cobalt-aluminium, son procédé de préparation et son utilisation dans un convertisseur catalytique

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CN101367045B (zh) * 2008-10-10 2011-02-09 天津大学 一种铜锰复合氧化物催化剂及其制备方法和应用
US20140336044A1 (en) * 2013-05-10 2014-11-13 Cdti Copper-Manganese Spinel Catalysts and Methods of Making Same
CN103599793A (zh) * 2013-11-28 2014-02-26 天津市环境保护科学研究院 室温去除甲醛的负载型铜锰复合氧化物催化剂及制备方法
CN111266115A (zh) * 2018-12-04 2020-06-12 河北工程大学 一种制备霍加拉特催化剂的方法
CN109569642B (zh) * 2018-12-13 2020-08-11 重庆工商大学 一种含铜-锰的双组分氧化物的共沉淀制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019204127A1 (fr) * 2018-04-20 2019-10-24 Aether Catalyst Solutions, Inc. Catalyseur d'oxydes métalliques mixtes à base de cuivre-cobalt-aluminium, son procédé de préparation et son utilisation dans un convertisseur catalytique
CN109621967A (zh) * 2018-12-26 2019-04-16 西安向阳航天材料股份有限公司 一种铜系低温变换催化剂的制备方法

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