WO2024066032A1 - Preparation method for modified hopcalite catalyst and use thereof - Google Patents

Preparation method for modified hopcalite catalyst and use thereof Download PDF

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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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French (fr)
Chinese (zh)
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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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    • 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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Abstract

The present invention provides a modified hopcalite catalyst, a preparation method therefor and a use thereof. The preparation method for the modified hopcalite catalyst comprises: mixing solutions containing a copper source, a manganese source, and an aluminum source to obtain a mixed solution; co-precipitating the mixed solution under an alkaline condition to obtain a precipitate; and roasting the obtained precipitate to finally obtain a modified hopcalite catalyst. According to the modified hopcalite catalyst provided by the present invention, by doping Al, Al, Cu and Mn form a new spinel structure which functions as a carrier, such that more Cu2+ and Mn4+ are dispersed on the surface of the catalyst. The catalyst has a stable structure, good low-temperature catalytic activity, and high catalytic stability. The preparation method provided by the present invention has a simple process and high product stability.

Description

一种改性霍加拉特催化剂的制备方法及应用Preparation method and application of modified hopcalite catalyst 技术领域Technical Field
本发明涉及催化燃烧CO用催化剂的技术领域。The present invention relates to the technical field of catalysts for catalytic combustion of CO.
背景技术Background technique
工业生产及工程作业实践中表明，设备在不完全燃烧的状态下会产生大量的CO。无色、无味的CO气体极易与人体血液中的血红蛋白进行结合，使得大脑缺氧进而产生偏瘫、失语乃至死亡等极其严重的不可逆后果。常见于燃煤锅炉、工厂车间等机器运转及材料氧化分解的应用场景中一氧化碳中毒事故频发，使得CO的处理成为目前急需解决的问题。Industrial production and engineering operation practices show that equipment will produce a large amount of CO in an incomplete combustion state. The colorless and odorless CO gas easily combines with hemoglobin in human blood, causing brain hypoxia and resulting in extremely serious irreversible consequences such as hemiplegia, aphasia and even death. Carbon monoxide poisoning accidents are common in coal-fired boilers, factory workshops and other machine operation and material oxidation and decomposition scenarios, making the treatment of CO an urgent problem to be solved.
目前成熟应用于CO催化燃烧的催化剂主要为贵金属催化剂，但高昂的成本极大地限制了贵金属催化剂的市场化应用，因此开发高低温活性、高稳定性、低成本的非贵金属催化剂将极大地推动催化燃烧市场化应用进程。Currently, the catalysts that are maturely used in CO catalytic combustion are mainly precious metal catalysts. However, 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.
在非贵金属催化剂中，以Cu、Mn氧化物及其复合氧化物为主要成分的霍加拉特催化剂在催化燃烧活性考察中表现出了较高的反应活性。以MnO 2和CuO为主要成分的Hopcalite催化剂广泛应用于潜水艇封闭仓中，在320℃的燃烧器环境内可以将CO高温催化为CO 2，该反应有无二次有毒污染物产生等优点(Christopher et al.Applied Catalysis B:Environmental,2017,(203)533-540)。现有的霍加拉特催化剂是以Cu、Mn形成的CuMn 2O 4尖晶石组成，这使得大部分Cu、Mn元素主要以载体形式存在于催化剂中，而只有少量Cu 2+及Mn 4+可以分散游离到催化剂表面形成催化反应活性中心，从而使得霍加拉特催化剂难以取得较好的低温催化活性。 Among non-precious metal catalysts, 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). Existing 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.
发明内容Summary of the invention
本发明的目的在于提供一种改性霍加拉特催化剂，Al的掺杂与Cu、Mn形成了新的尖晶石结构从而起到了载体的作用，使得更多的Cu 2+及Mn 4+分散在催化剂表面。其结构稳定，低温催化活性好，催化稳定性高。本发明的目的还在于提供上述催化剂的制备方法，其过程简单，产物稳定性高。 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.
本发明的目的还在于提供上述催化剂的应用方法。The present invention also aims to provide an application method of the catalyst.
为实现上述目的之一，本发明提供了如下的技术方案：To achieve one of the above purposes, the present invention provides the following technical solutions:
一种改性霍加拉特催化剂，其包括以下组分：由CuAl 2O 4、MnAl 2O 4及Cu、Mn的氧化物组成的复合氧化物。 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.
根据本发明的一些具体实施方式，所述Cu、Mn的氧化物为CuMnO 2。 According to some specific embodiments of the present invention, the oxide of Cu and Mn is CuMnO 2 .
根据本发明的一些具体实施方式，所述复合氧化物中，Cu元素、Mn元素及Al元素的物质的量之比为1～10:1～10:0.2～5。According to some specific embodiments of the present invention, in the composite oxide, the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
优选的，所述Cu元素、Mn元素及Al元素的物质的量之比为5:1:0.2～3，进一步优选为5:1:0.5～1。Preferably, 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.
为实现上述目的之二，本发明提供了如下的技术方案：To achieve the second of the above objectives, the present invention provides the following technical solutions:
上述催化剂的制备方法，其包括以下过程：将含有Cu离子、Mn离子及Al离子的混合溶液进行共沉淀，将所得沉淀物进行焙烧。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.
根据本发明的一些具体实施方式，所述混合溶液为含有Cu的化合物、Mn的化合物及Al的化合物的酸溶液。According to some specific embodiments of the present invention, the mixed solution is an acid solution containing a Cu compound, a Mn compound and an Al compound.
优选的，所述酸溶液为硝酸溶液。Preferably, the acid solution is a nitric acid solution.
根据本发明的一些具体实施方式，所述焙烧温度为300～500□。According to some specific embodiments of the present invention, the calcination temperature is 300-500°C.
根据本发明的一些具体实施方式，所述焙烧时间为6～10h。According to some specific embodiments of the present invention, the calcination time is 6 to 10 hours.
根据本发明的一些具体实施方式，所述共沉淀在碱性条件下进行。According to some specific embodiments of the present invention, the coprecipitation is carried out under alkaline conditions.
优选的，所述碱性条件为pH＝8～9，进一步优选pH＝8～8.5。Preferably, the alkaline condition is pH=8-9, more preferably pH=8-8.5.
根据本发明的一些具体实施方式，所述共沉淀使用碱作为沉淀剂，所述碱选 自氢氧化钠、碳酸钠和氨水中的一种或多种。According to some specific embodiments of the present invention, 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.
根据本发明的一些具体实施方式，所述碱的浓度为0.3～3mol·L -1。 According to some specific embodiments of the present invention, the concentration of the base is 0.3 to 3 mol·L -1 .
优选的，所述碱的浓度为1.5～2.5mol·L -1。 Preferably, the concentration of the base is 1.5 to 2.5 mol·L -1 .
根据本发明的一些具体实施方式，所述共沉淀的温度为10～30□。According to some specific embodiments of the present invention, the coprecipitation temperature is 10 to 30 °C.
优选的，所述共沉淀温度为15～20□。Preferably, the coprecipitation temperature is 15-20℃.
根据本发明的一些具体实施方式，在共沉淀后将所述混合溶液进行10～20h的静置。According to some specific embodiments of the present invention, the mixed solution is allowed to stand for 10 to 20 hours after the coprecipitation.
根据本发明的一些具体实施方式，所述复合氧化物中，Cu元素、Mn元素及Al元素的物质的量之比为1～10:1～10:0.2～5。According to some specific embodiments of the present invention, in the composite oxide, the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
优选的，所述Cu元素、Mn元素及Al元素的物质的量之比为5:1:0.5～1。Preferably, the molar ratio of the Cu element, the Mn element and the Al element is 5:1:0.5-1.
根据本发明的一些具体实施方式，所述混合溶液中含有金属离子的总浓度为0.5～1.5mol·L -1。 According to some specific embodiments of the present invention, the total concentration of metal ions in the mixed solution is 0.5 to 1.5 mol·L -1 .
根据本发明的一些具体实施方式，所述Cu的化合物选自硝酸铜(Cu(NO 3) 2·3H 2O)和/或硫酸铜(CuSO 4)。 According to some specific embodiments of the present invention, the Cu compound is selected from copper nitrate (Cu(NO 3 ) 2 ·3H 2 O) and/or copper sulfate (CuSO 4 ).
根据本发明的一些具体实施方式，所述Mn的化合物选自硝酸锰(MnN 2O 6·4H 2O)和/或硝酸锰溶液(Mn(NO 3) 2)。 According to some specific embodiments of the present invention, the Mn compound is selected from manganese nitrate (MnN 2 O 6 ·4H 2 O) and/or manganese nitrate solution (Mn(NO 3 ) 2 ).
根据本发明的一些具体实施方式，所述Al的化合物选自硝酸铝(Al(NO 3) 3·9H 2O)。 According to some specific embodiments of the present invention, the Al compound is selected from aluminum nitrate (Al(NO 3 ) 3 ·9H 2 O).
根据本发明的一些具体实施方式，所述混合溶液的制备包括：将所述铜源、锰源、铝源依次溶解于蒸馏水后得到所述混合溶液。According to some specific embodiments of the present invention, 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.
为实现上述目的之三，本发明提供了如下的技术方案：To achieve the third objective above, the present invention provides the following technical solutions:
将上述催化剂或根据上述制备方法制备得到的催化剂应用于CO催化燃烧的应用。The catalyst or the catalyst prepared according to the preparation method is applied to CO catalytic combustion.
根据本发明的一些具体实施方式，所述催化剂的粒径为20-60目。According to some specific embodiments of the present invention, the particle size of the catalyst is 20-60 mesh.
具体地，上述应用中，CO低温氧化温度为20℃。Specifically, in the above application, the CO low temperature oxidation temperature is 20°C.
本发明具备以下有益效果：The present invention has the following beneficial effects:
(1)本发明获得了一种新型的CO催化燃烧用霍加拉特催化剂；(1) The present invention obtains a novel hopcalite catalyst for catalytic combustion of CO;
(2)相对于现有技术中的霍加拉特催化剂，本发明在已存在霍加拉特催化剂中还进行了Al 2O 3的掺杂，在提高活性中心组分Cu 2+、Mn 4+分散度的同时，金属离子的掺杂效应进一步促进了CO与Cu、Mn之间的结合强度，使得催化剂的低温活性、催化效率得到了显著的提升； (2) Compared with the hopcalite catalyst in the prior art, 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;
(3)本发明的催化剂在用于CO催化燃烧反应中的低温活性表现要优于传统霍加拉特催化剂，在20℃的室温条件下即可实现CO的100％转化；(3) 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;
(4)Al的掺杂在提升催化剂低温催化活性的同时，进一步降低了霍加拉特催化剂的制备成本，共沉淀的制备工艺路线操作简单，可行性较强；(4) Al doping not only improves the low-temperature catalytic activity of the catalyst, but also further reduces the preparation cost of the hopcalite catalyst. The co-precipitation preparation process is simple to operate and has strong feasibility.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例5的XRD谱图；FIG. 1 is an XRD spectrum of Example 5;
图2为实施例5与商业霍贾拉特催化剂的H2-TPR对比图。FIG. 2 is a comparison chart of H2-TPR of Example 5 and commercial Hojalat catalyst.
具体实施方式Detailed ways
以下结合实施例本发明进行详细描述，但需要理解的是，所述实施例和附图仅用于对本发明进行示例性的描述，而并不能对本发明的保护范围构成任何限制。所有包含在本发明的发明宗旨范围内的合理的变换和组合均落入本发明的保护范围。The present invention is described in detail below in conjunction with the embodiments, but it should be understood that the embodiments and drawings are only used to exemplify the present invention and do not constitute any limitation on the protection scope of the present invention. All reasonable changes and combinations included in the scope of the invention spirit of the present invention fall within the protection scope of the present invention.
以下各实施例使用的催化剂通过以下制备过程获得：The catalyst used in the following examples was obtained by the following preparation process:
称取并加入适量硝酸铜、硝酸锰、硝酸铝加入适量蒸馏水中，进行充分搅拌混合，得到清澈透明的金属离子混合溶液，其中各原料的用量满足Cu:Mn:Al 的摩尔比为5:1:x，x＝0～1；所得混合溶液中金属离子总浓度控制为1mol·L -1。以2mol·L -1的NaOH溶液为沉淀剂，在搅拌条件下，同时将金属离子混合液和NaOH沉淀剂滴加至5L的烧杯，进行共沉淀反应，反应温度选择常温、pH＝8～8.5，滴定过程中，通过调节二者滴速以调节反应液的pH值。待金属离子溶液滴加完时，立即停止滴加NaOH沉淀剂，并继续在常温下搅拌2h、静置老化15h。所得沉淀物经过滤、洗涤至pH＝7左右，所得滤饼于100℃空气中干燥、其后400℃焙烧6～10h，得到CuO-MnO 2-xAl 2O 3催化剂，将筛分后的20-60目的催化剂颗粒用于固定床CO催化燃烧反应。 Weigh and add appropriate amount of copper nitrate, manganese nitrate and aluminum nitrate to appropriate amount of distilled water, stir and mix thoroughly to obtain a clear and transparent metal ion mixed solution, wherein the amount of each raw material satisfies the molar ratio of Cu:Mn:Al of 5:1:x, x=0~1; the total concentration of metal ions in the obtained mixed solution is controlled to be 1mol·L -1 . Using 2mol·L -1 NaOH solution as a precipitant, under stirring conditions, the metal ion mixed solution and NaOH precipitant are simultaneously added dropwise to a 5L beaker for coprecipitation reaction. The reaction temperature is selected to be room temperature and pH=8~8.5. During the titration process, the pH value of the reaction solution is adjusted by adjusting the dripping rate of the two. When the metal ion solution is added, stop adding the NaOH precipitant immediately, continue stirring at room temperature for 2h, and let it stand for aging for 15h. The obtained precipitate was filtered and washed to pH=7, the filter cake was dried in air at 100°C, and then calcined at 400°C for 6-10h to obtain CuO- MnO2 - xAl2O3 catalyst, and the sieved catalyst particles of 20-60 mesh were used for fixed bed CO catalytic combustion reaction.
以下各实施例使用固定床CO催化燃烧反应的过程为：The following embodiments use the fixed bed CO catalytic combustion reaction process as follows:
将5g筛分后的催化剂颗粒装填于固定床反应器，预先用空气在350℃下预活化6h左右，而后将床层温度调至所需反应温度，并将CO以30mL·min -1的气速率通过质量流量计通入固定床反应器，进行催化燃烧反应，反应产物气直接进入气相色谱中进行检测，催化燃烧反应的考察温度范围为20-200℃，考察的CuO-MnO 2-xAl 2O 3催化剂中Al掺杂量(以金属离子Al/(Cu+Mn)％计)范围为0～30％。 5 g of sieved catalyst particles are loaded into a fixed bed reactor, pre-activated with air at 350°C for about 6 hours, and then the bed temperature is adjusted to the required reaction temperature, and CO is introduced into the fixed bed reactor through a mass flow meter at a gas rate of 30 mL·min -1 to carry out a catalytic combustion reaction. The reaction product gas directly enters a gas chromatograph for detection. The temperature range of the catalytic combustion reaction is 20-200°C, and the Al doping amount (in terms of metal ion Al/(Cu+Mn)%) in the investigated CuO- MnO2 -xAl2O3 catalyst ranges from 0 to 30%.
实施例1Example 1
对商业霍加拉特催化剂进行CO催化燃烧反应活性考察。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析，评价反应物CO转化率公式如下： The activity of CO catalytic combustion reaction was investigated on commercial hopcalite catalyst. In a fixed bed reactor, 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:
X CO(％)＝([CO] in-[CO] out)/[CO] in*100％ XCO (%)＝([CO] in -[CO] out )/[CO] in *100%
X CO:CO转化率；[CO] in：反应器入口CO浓度；[CO] out：反应器出口CO浓度； XCO : CO conversion rate; [CO] in : CO concentration at reactor inlet; [CO] out : CO concentration at reactor outlet;
在三次采样结果误差小于1％的条件下结束该温度下的采集，取三次采样平均转化率作为该温度下的转化率。而后以5℃/次升温，直至CO转化率到达100％反应终止。When the error of three sampling results is less than 1%, 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.
反应结果显示，在125℃下混合器通入催化剂床层后，CO转化率达到100％。The reaction results showed that the CO conversion rate reached 100% after the mixer was introduced into the catalyst bed at 125°C.
实施例2Example 2
以Cu:Mn:Al的摩尔比＝5:1:0.2制备Cu-Mn-Al复合氧化物作为催化剂。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析。 Cu-Mn-Al composite oxide was prepared as a catalyst with a molar ratio of Cu:Mn:Al = 5:1:0.2. 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.
反应结果显示，在85℃下混合器通入催化剂床层后，CO转化率达到100％。The reaction results showed that the CO conversion rate reached 100% after the mixer was introduced into the catalyst bed at 85°C.
实施例3Example 3
以Cu:Mn:Al的摩尔比＝5:1:0.4制备Cu-Mn-Al复合氧化物作为催化剂。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析。 Cu-Mn-Al composite oxide was prepared as a catalyst with a molar ratio of Cu:Mn:Al = 5:1:0.4. 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.
反应结果显示，在55℃下混合器通入催化剂床层后，CO转化率达到100％。The reaction results showed that the CO conversion rate reached 100% after the catalyst bed was introduced into the mixer at 55°C.
实施例4Example 4
以Cu:Mn:Al的摩尔比＝5:1:0.6制备Cu-Mn-Al复合氧化物作为催化剂。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析。 Cu-Mn-Al composite oxide was prepared as a catalyst with a molar ratio of Cu:Mn:Al = 5:1:0.6. 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.
反应结果显示，在35℃下混合器通入催化剂床层后，CO转化率达到100％The reaction results showed that the CO conversion rate reached 100% after the catalyst bed was introduced into the mixer at 35°C.
实施例5Example 5
以Cu:Mn:Al的摩尔比＝5:1:0.8制备Cu-Mn-Al复合氧化物作为催化剂。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析。 Cu-Mn-Al composite oxide was prepared as a catalyst with a molar ratio of Cu:Mn:Al = 5:1:0.8. 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.
反应结果显示，在20℃下混合器通入催化剂床层后，CO转化率达到100％。The reaction results showed that the CO conversion rate reached 100% after the catalyst bed was introduced into the mixer at 20°C.
实施例6Example 6
以Cu:Mn:Al的摩尔比＝5:1:1制备Cu-Mn-Al复合氧化物作为催化剂。在固定床反应器中，以30mL·min -1速率通入由1.6％CO、21.4％的氧气、77.0％的氮气组成的混合气，反应空速360h -1、常压、反应温度15℃条件下，进行CO催化燃烧反应，待温度稳定后15min开始采集，在SC-2000型气象色谱仪上进行TCD检测器的在线分析。 Cu-Mn-Al composite oxide was prepared as a catalyst with a molar ratio of Cu:Mn:Al = 5:1:1. 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.
反应结果显示，在45℃下混合器通入催化剂床层后，CO转化率达到100％。The reaction results showed that the CO conversion rate reached 100% after the mixer was introduced into the catalyst bed at 45°C.
实施例7Example 7
主要考察了商业性霍贾拉特催化剂以及Cu:Mn:Al的摩尔比分别为5:1:0.2，5:1:0.4，5:1:0.6，5:1:0.8，5:1:1制备Cu-Mn-Al复合氧化物。对低温活性最好的实施例5中催化剂通过X射线衍射进行表征，得到如附图1所示的XRD谱图，从图中可以看出，Cu-Mn-Al催化剂中的主要晶型为Cu、Mn、Al三种元素相互结合生成尖晶石的结构，同时观察到有一部分生成CuMnO 2复合氧化物，这表明在Al元素加入后新生成的Cu-Mn-Al复合氧化物催化剂中，Al作为载体使得CuMn 2O 4尖晶石结构被CuAl 2O 4和MnAl 2O 4所取代，这使得Cu、Mn分散度增加从而得到了更好的催化活性。H 2-TPR的结果也同样验证了这个规律。对实施例5中 催化剂与商业霍加拉特催化剂通过H 2程序升温还原进行表征，得到如附图2所示的H 2-TPR对比谱图，从图中可以看出，Al的掺杂使得Cu-Mn催化剂更容易被还原，这进一步证明催化剂中Cu 2+、Mn 2+分散度的增加，同时Al的掺杂有效地降低了活性成分与载体之间的相互作用，使得活性组分游离态Cu 2+、Mn 4+在催化剂表面上分散程度增大，增强了催化剂的低温还原性，从而提高了催化燃烧的反应活性。 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. It can be seen from the figure that 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. It can be seen from the figure that 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. At the same time, 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.
以上实施例仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。凡属于本发明思路下的技术方案均属于本发明的保护范围。应该指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下的改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above embodiments are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims (14)

  1. 一种改性霍加拉特催化剂的制备方法，其特征在于，包括以下步骤：A method for preparing a modified hopcalite catalyst, characterized in that it comprises the following steps:
    将含有铜源、锰源、铝源的溶液混合，得到混合溶液；Mixing solutions containing a copper source, a manganese source, and an aluminum source to obtain a mixed solution;
    将所述混合溶液在碱性条件下进行共沉淀，得到沉淀物；co-precipitating the mixed solution under alkaline conditions to obtain a precipitate;
    将所得沉淀物进行焙烧，最终制得所述改性霍加拉特催化剂；calcining the obtained precipitate to finally obtain the modified hopcalite catalyst;
    其中，将所述混合溶液在碱性条件下进行共沉淀的温度为10-30℃。Wherein, the temperature for co-precipitation of the mixed solution under alkaline conditions is 10-30°C.
  2. 根据权利要求1所述的改性霍加拉特催化剂的制备方法，其特征在于，The method for preparing the modified hopcalite catalyst according to claim 1, characterized in that:
    所述铜源为含有Cu离子的化合物酸溶液；The copper source is a compound acid solution containing Cu ions;
    所述锰源为含有Mn离子的化合物的酸溶液；The manganese source is an acid solution of a compound containing Mn ions;
    所述铝源为含有Al离子的化合物的酸溶液。The aluminum source is an acid solution of a compound containing Al ions.
  3. 根据权利要求2所述的改性霍加拉特催化剂的制备方法，所述Cu离子的化合物酸溶液包括：硝酸铜和/或硫酸铜。According to the method for preparing a modified hopcalite catalyst according to claim 2, the compound acid solution of Cu ions comprises: copper nitrate and/or copper sulfate.
  4. 根据权利要求2所述的改性霍加拉特催化剂的制备方法，所述含有Mn离子的化合物的酸溶液包括：硝酸锰。According to the method for preparing a modified hopcalite catalyst according to claim 2, the acid solution of the compound containing Mn ions comprises: manganese nitrate.
  5. 根据权利要求2所述的改性霍加拉特催化剂的制备方法，所述有Al离子的化合物的酸溶液包括：硝酸铝。According to the method for preparing a modified hopcalite catalyst according to claim 2, the acid solution of the compound having Al ions comprises: aluminum nitrate.
  6. 根据权利要求1-5任一所述的改性霍加拉特催化剂的制备方法，其特征在于，所述铜源中Cu元素、所述锰源中Mn元素、所述铝源中Al元素的物质的量之比为(1-10):(1-10):(0.2-5)。The method for preparing a modified hopcalite catalyst according to any one of claims 1 to 5, characterized in that the molar ratio of the Cu element in the copper source, the Mn element in the manganese source, and the Al element in the aluminum source is (1-10):(1-10):(0.2-5).
  7. 根据权利要求6所述的改性霍加拉特催化剂的制备方法，其特征在于，所述铜源中Cu元素、所述锰源中Mn元素、所述铝源中 Al元素的物质的量之比为5:1:(0.2-1)。The method for preparing a modified hopcalite catalyst according to claim 6, characterized in that the molar ratio of the Cu element in the copper source, the Mn element in the manganese source, and the Al element in the aluminum source is 5:1:(0.2-1).
  8. 根据权利要求7所述的改性霍加拉特催化剂的制备方法，其特征在于，所述铜源中Cu元素、所述锰源中Mn元素、所述铝源中Al元素的物质的量之比为5:1:(0.5-1)。The method for preparing a modified hopcalite catalyst according to claim 7, characterized in that the molar ratio of the Cu element in the copper source, the Mn element in the manganese source, and the Al element in the aluminum source is 5:1:(0.5-1).
  9. 根据权利要求1-5任一所述的改性霍加拉特催化剂的制备方法，其特征在于，所述焙烧温度为300-500℃；焙烧时间为6-10h。The method for preparing a modified hopcalite catalyst according to any one of claims 1 to 5, characterized in that the calcination temperature is 300-500° C. and the calcination time is 6-10 h.
  10. 根据权利要求1-5任一所述的改性霍加拉特催化剂的制备方法，其特征在于，所述碱性条件包括:pH＝8-9，使用碱作为沉淀剂,碱的浓度为1-3mol/L。The method for preparing a modified hopcalite catalyst according to any one of claims 1 to 5, characterized in that the alkaline conditions include: pH = 8-9, using a base as a precipitant, and the concentration of the base is 1-3 mol/L.
  11. 根据权利要求1-5任一所述的改性霍加拉特催化剂的制备方法，其特征在于，将所述混合溶液在碱性条件下进行共沉淀的温度为15-20℃。The method for preparing a modified hopcalite catalyst according to any one of claims 1 to 5, characterized in that the temperature at which the mixed solution is coprecipitated under alkaline conditions is 15-20°C.
  12. 根据权利要求1-5任一所述的改性霍加拉特催化剂的制备方法，其特征在于，在将所述混合溶液在碱性条件下进行共沉淀后静置10～20h，得到所述沉淀物。The method for preparing a modified hopcalite catalyst according to any one of claims 1 to 5, characterized in that the mixed solution is allowed to stand for 10 to 20 hours after coprecipitation under alkaline conditions to obtain the precipitate.
  13. 一种权利要求1-12任一所述的制备方法制备得到的改性霍加拉特催化剂。A modified hopcalite catalyst prepared by the preparation method according to any one of claims 1 to 12.
  14. 权利要求13所述的改性霍加拉特催化剂在CO催化燃烧中的应用。Use of the modified hopcalite catalyst according to claim 13 in catalytic combustion of CO.
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