CN105498780A - A kind of Cu/ZnO catalyst and its preparation method and application in CO2 chemical conversion - Google Patents

A kind of Cu/ZnO catalyst and its preparation method and application in CO2 chemical conversion Download PDF

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CN105498780A
CN105498780A CN201510990534.8A CN201510990534A CN105498780A CN 105498780 A CN105498780 A CN 105498780A CN 201510990534 A CN201510990534 A CN 201510990534A CN 105498780 A CN105498780 A CN 105498780A
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蔡伟杰
张绍印
崔励
张江华
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Sichuan Hydrogen Carbon Oxygen Technology Co ltd
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Abstract

本发明公开了一种Cu/ZnO催化剂及其制备方法和在CO2化学转化中的应用，属于催化及温室气体CO2减排领域。Cu/ZnO催化剂的制备方法为：将可溶性锌盐和六次甲基四胺溶于乙二醇水溶液中；惰性气氛下，微波反应器中功率200～300W反应合成ZnO载体；利用沉积沉淀法将活性金属铜担载在合成的ZnO载体上。合成的ZnO载体具有均一的花状或纳米棒形貌，Cu担载量为5～15wt％。该催化剂在CO2催化转化合成低碳醇反应中表现出高活性和稳定性。本发明合成的催化剂具有工艺简单、成本低、催化性能高等优点，符合绿色化工的发展趋势；并且在CO2化学转化合成重要化学品领域具有广阔的应用前景。The invention discloses a Cu/ZnO catalyst, a preparation method thereof and an application in CO2 chemical conversion, belonging to the fields of catalysis and greenhouse gas CO2 emission reduction. The preparation method of Cu/ZnO catalyst is as follows: dissolving soluble zinc salt and hexamethylenetetramine in ethylene glycol aqueous solution; under inert atmosphere, the power of microwave reactor is 200-300W to react to synthesize ZnO carrier; The active metal copper is supported on the synthesized ZnO support. The synthesized ZnO carrier has a uniform flower-like or nanorod morphology, and the Cu loading is 5-15wt%. The catalyst exhibited high activity and stability in the catalytic conversion of CO to lower alcohols. The catalyst synthesized by the invention has the advantages of simple process, low cost, high catalytic performance, etc., conforms to the development trend of green chemical industry, and has broad application prospects in the field of CO2 chemical conversion and synthesis of important chemicals.

Description

一种Cu/ZnO催化剂及其制备方法和在CO2化学转化中的应用A kind of Cu/ZnO catalyst and its preparation method and application in CO2 chemical conversion

技术领域technical field

本发明涉及一种Cu/ZnO催化剂及其制备方法和在CO2化学转化中的应用，属于催化化学和温室气体减排领域。The invention relates to a Cu/ZnO catalyst, a preparation method thereof and an application in CO2 chemical conversion, belonging to the fields of catalytic chemistry and greenhouse gas emission reduction.

背景技术Background technique

温室气体CO2主要来源于化石资源的燃烧排放,随着现代工业的迅速发展，大气中CO2浓度越来越高,导致温室效应、全球温度升高，严重影响人类生产、生活。降低CO2大气中含量成为目前研究的热点领域之一。基于CO2是一种廉价、丰富的C1资源考虑，将CO2作为碳氧资源使用，利用化学转化合成高附加值化学品是解决CO2对环境影响的重要途径，也是解决长期以来化学品严重依赖不可再生资源化石燃料的有效措施，与传统的CO2捕获、分离、埋存等处理技术相比具有更重要的社会和经济意义。甲醇是一种重要的有机化工原料，是C1化工的基础，也是一种良好的有机溶剂和有望替代汽油的液体燃料。利用CO2加氢合成甲醇既能够减少或维持大气中CO2浓度，又能得到重要的能源载体甲醇，是一条“一举两得、变废为宝”的技术路线，因此其研究倍受关注。由于CO2的热力学稳定性和化学惰性，实现CO2加氢合成甲醇工艺路线的关键在于构建设计高活性、高稳定性催化剂。近年来CO2加氢制甲醇催化剂体系主要以铜系和贵金属体系(Pt，Ru等)为主。虽然贵金属催化剂具有较高活性和选择性，但价格高昂、活性温度范围窄等缺点成为制约其广泛应用的瓶颈问题。The greenhouse gas CO 2 mainly comes from the combustion of fossil resources. With the rapid development of modern industry, the concentration of CO 2 in the atmosphere is getting higher and higher, which leads to the greenhouse effect and global temperature rise, which seriously affects human production and life. Reducing the content of CO 2 in the atmosphere has become one of the hot research areas at present. Considering that CO 2 is a cheap and abundant C 1 resource, using CO 2 as a carbon-oxygen resource and using chemical conversion to synthesize high-value-added chemicals is an important way to solve the impact of CO 2 on the environment. Effective measures that rely heavily on non-renewable resource fossil fuels have more important social and economic significance than traditional CO2 treatment technologies such as capture, separation, and storage. Methanol is an important organic chemical raw material, the basis of C 1 chemical industry, a good organic solvent and a liquid fuel that is expected to replace gasoline. The use of CO 2 hydrogenation to synthesize methanol can not only reduce or maintain the concentration of CO 2 in the atmosphere, but also obtain methanol, an important energy carrier. Due to the thermodynamic stability and chemical inertness of CO 2 , the key to realize the process route of CO 2 hydrogenation to methanol lies in the construction and design of catalysts with high activity and high stability. In recent years, the catalyst systems for CO2 hydrogenation to methanol are mainly copper-based and noble metal-based (Pt, Ru, etc.). Although noble metal catalysts have high activity and selectivity, the disadvantages of high price and narrow activity temperature range have become bottlenecks restricting their wide application.

过渡金属铜基催化剂，以其高活性、低成本成为国内外研究热点。但铜基催化剂在反应过程中活性铜表面积易降低、活性组分流失,催化剂易失活抑制其广泛工业化应用。构建设计高效稳定铜基催化剂，抑制反应过程中活性Cu组分的流失，对CO2加氢催化剂的开发具有重要的促进意义，其中蕴含的科学难题值得我们深入探索。Transition metal copper-based catalysts have become a research hotspot at home and abroad because of their high activity and low cost. However, the active copper surface area of copper-based catalysts is easy to decrease during the reaction process, the active components are lost, and the catalyst is easily deactivated, which inhibits its wide industrial application. The construction and design of efficient and stable copper-based catalysts, which can inhibit the loss of active Cu components during the reaction process, is of great significance to the development of CO2 hydrogenation catalysts, and the scientific problems contained in it are worthy of our in-depth exploration.

近期纳米材料科学研究证明纳米催化剂的催化性能不仅受尺寸效应影响，还跟催化剂的形貌密切相关。形貌各异的纳米材料表面优先暴露的晶面不同，表面的原子组成、配位模式、电子结构会发生显著变化，因此吸附和活化反应物的能力会有所差异，导致不同的催化反应性能，即纳米催化中的形貌效应。纳米尺度下的催化材料可控合成以及对其真实反应气氛下构-效关系的认识是纳米催化的关键问题。传统的水热、溶剂热技术可以通过选择前驱体，利用离子缓释剂和结构导向剂等，精确调变制备参数,在一定程度上获得形貌可控的固体催化剂。利用微波技术合成特定形貌催化剂与传统加热技术相比，微波加热速度快、加热均匀、节能高效、设备简单、易于控制。Recent scientific research on nanomaterials has proved that the catalytic performance of nanocatalysts is not only affected by the size effect, but also closely related to the morphology of the catalyst. The surface of nanomaterials with different shapes has different preferentially exposed crystal planes, and the atomic composition, coordination mode, and electronic structure of the surface will change significantly, so the ability to adsorb and activate reactants will be different, resulting in different catalytic performance. , that is, the morphology effect in nanocatalysis. The controllable synthesis of catalytic materials at the nanoscale and the understanding of their structure-property relationships in real reaction atmospheres are key issues in nanocatalysis. Traditional hydrothermal and solvothermal technologies can precisely adjust the preparation parameters by selecting precursors, using ion slow-release agents and structure-directing agents, etc., to obtain solid catalysts with controllable morphology to a certain extent. Using microwave technology to synthesize catalysts with specific morphology compared with traditional heating technology, microwave heating speed, uniform heating, energy saving and high efficiency, simple equipment, easy to control.

国内外对于特定形貌CO2加氢催化剂的研究鲜有文献报道，而且特定形貌担载型铜基催化剂应用于CO2化学转化领域未见专利报道。There are few literature reports on the research on specific morphology CO 2 hydrogenation catalysts at home and abroad, and there are no patent reports on the application of specific morphology supported copper-based catalysts in the field of CO 2 chemical conversion.

发明内容Contents of the invention

本发明采用微波热解法合成形貌均一ZnO纳米材料，通过改变载体形貌优先暴露高活性晶面，进而提高活性中心的表面密度，以此为基础构建设计担载型铜基催化剂，利用调变ZnO载体和活性金属Cu粒子的形貌尺寸，增强催化剂活化CO2能力以及金属--载体间的相互作用程度，提高活性Cu组分的稳定性。该催化剂应用于CO2加氢制甲醇反应体系，表现出高活性、高稳定性。The invention adopts the microwave pyrolysis method to synthesize ZnO nanomaterials with uniform appearance, and by changing the shape of the carrier to preferentially expose the high-activity crystal face, thereby increasing the surface density of the active center, and constructing and designing a supported copper-based catalyst based on this, and utilizing the adjusted Change the shape and size of ZnO support and active metal Cu particles, enhance the catalyst's ability to activate CO 2 and the degree of interaction between metal and support, and improve the stability of active Cu components. The catalyst is applied in the reaction system of CO2 hydrogenation to methanol, showing high activity and high stability.

本发明通过以下技术方案实现：本发明提供一种Cu/ZnO催化剂，以Cu为活性组分，ZnO氧化物为载体；催化剂中活性组分含量为10～15wt％；催化剂中ZnO载体具有均一的纳米花状和/或纳米棒形貌，Cu粒子平均粒径为10～25nm。The present invention is achieved through the following technical solutions: the present invention provides a Cu/ZnO catalyst, with Cu as the active component and ZnO oxide as the carrier; the content of the active component in the catalyst is 10 to 15 wt%; the ZnO carrier in the catalyst has a uniform Nanoflower and/or nanorod morphology, the average particle size of Cu particles is 10-25nm.

本发明提供一种上述Cu/ZnO催化剂的制备方法，包括以下步骤：The present invention provides a kind of preparation method of above-mentioned Cu/ZnO catalyst, comprises the following steps:

(1)室温条件下将可溶性锌盐和六次甲基四胺按照摩尔比1:0.5～3溶于10～20wt％的乙二醇水溶液中；惰性气体气氛下，微波反应器中功率200～300W反应10～15分钟；降至室温，沉淀抽滤、用热去离子水洗涤至中性、90°下干燥12h；合成ZnO载体；(1) Under room temperature conditions, soluble zinc salt and hexamethylenetetramine are dissolved in 10 to 20 wt% ethylene glycol aqueous solution according to the molar ratio of 1:0.5 to 3; under an inert gas atmosphere, the power in the microwave reactor is 200 to React at 300W for 10-15 minutes; cool down to room temperature, filter the precipitate with suction, wash with hot deionized water until neutral, and dry at 90° for 12 hours; synthesize ZnO carrier;

(2)室温条件下将可溶性铜盐和上述步骤(1)制备的ZnO载体按照质量比1～4:2～11加入100-300mL去离子水中；搅拌加热至60～80℃，缓慢滴加0.1～0.3mol/LNa2CO3或K2CO3溶液至pH为9～10，进一步搅拌老化1～3h，沉淀抽滤、用热去离子水洗涤至中性、90°下干燥12h，在400～600℃下于马弗炉中焙烧4～8h；合成负载型Cu/ZnO催化剂。(2) Add the soluble copper salt and the ZnO carrier prepared in the above step (1) into 100-300mL deionized water according to the mass ratio of 1~4:2~11 at room temperature; stir and heat to 60~80°C, slowly add 0.1 ～0.3mol/LNa 2 CO 3 or K 2 CO 3 solution until the pH is 9～10, further stirred and aged for 1～3h, precipitated and filtered, washed with hot deionized water until neutral, dried at 90° for 12h, and dried at 400°C Baking in a muffle furnace at ~600°C for 4-8 hours; synthesizing a supported Cu/ZnO catalyst.

进一步地，在上述技术方案中，步骤(1)中，可溶性锌盐和六次甲基四胺摩尔比为1:0.5～1.5；优选1:1；得到的催化剂中ZnO载体具有均一的纳米棒形貌；长度为2000～3000nm；直径10～30nm。Further, in the above technical scheme, in step (1), the molar ratio of the soluble zinc salt to hexamethylenetetramine is 1:0.5 to 1.5; preferably 1:1; the ZnO carrier in the obtained catalyst has a uniform nanorod Morphology; length 2000-3000nm; diameter 10-30nm.

进一步地，在上述技术方案中，步骤(1)中，可溶性锌盐和六次甲基四胺摩尔比为1:2～3；优选1:3；得到的催化剂中ZnO载体具有均一的纳米花状形貌；花瓣为棒状，花瓣长度为300～600nm；直径20～40nm。Further, in the above technical scheme, in step (1), the molar ratio of the soluble zinc salt to hexamethylenetetramine is 1:2 to 3; preferably 1:3; the ZnO carrier in the obtained catalyst has uniform nanoflowers shape; the petals are rod-shaped, the petal length is 300-600nm; the diameter is 20-40nm.

进一步地，在上述技术方案中，步骤(1)中所述可溶性锌盐选自Zn(NO3)2.6H2O，ZnCl2等。Further, in the above technical solution, the soluble zinc salt in step (1) is selected from Zn(NO 3 ) 2 .6H 2 O, ZnCl 2 and the like.

进一步地，在上述技术方案中，所述惰性气体为氮气，氦气，氩气等。Further, in the above technical solution, the inert gas is nitrogen, helium, argon and the like.

进一步地，在上述技术方案中，步骤(2)中所述可溶性铜盐选自Cu(NO3)2，CuSO4，CuCl2等。Further, in the above technical solution, the soluble copper salt in step (2) is selected from Cu(NO 3 ) 2 , CuSO 4 , CuCl 2 and the like.

本发明提供上述催化剂在CO2催化转化合成低碳醇反应中的应用。The invention provides the application of the above-mentioned catalyst in the reaction of catalytic conversion of CO2 to synthesize low-carbon alcohols.

进一步地，在上述应用中，利用传统固定床反应器，将0.1～0.5g(40～60目)催化剂加入不锈钢反应管(300mm长,直径9mm，316型不锈钢)中，添加石英砂至催化剂床层0.5～2.0cm；反应温度250～270℃,反应压力30～45bar，反应气(CO2/H2＝1/3,摩尔比)流速为66～133mL/min，反应空速为2000～4000h-1。Further, in the above application, using a traditional fixed-bed reactor, add 0.1-0.5g (40-60 mesh) catalyst into a stainless steel reaction tube (300mm long, 9mm in diameter, 316 stainless steel), add quartz sand to the catalyst bed Layer 0.5～2.0cm; reaction temperature 250～270℃, reaction pressure 30～45bar, reaction gas (CO 2 /H 2 =1/3, molar ratio) flow rate 66～133mL/min, reaction space velocity 2000～4000h -1 .

发明有益效果Beneficial effect of the invention

(1)能耗低：微波技术属于体加热，与常规加热方法相比具有反应体系受热均匀、促进反应分子间的碰撞几率、缩短反应时间、反应温度低消耗能量较少等优点。(1) Low energy consumption: Microwave technology belongs to body heating. Compared with conventional heating methods, it has the advantages of uniform heating of the reaction system, promotion of collision probability between reaction molecules, shortened reaction time, low reaction temperature and less energy consumption.

(2)反应活性及稳定性高，不宜失活：金属Cu与载体ZnO之间的强相互作用有利于抑制反应过程中活性Cu组分比表面积降低，增强催化剂稳定性。(2) High reactivity and stability, not suitable for deactivation: the strong interaction between metal Cu and support ZnO is beneficial to suppress the reduction of the specific surface area of the active Cu component during the reaction process, and enhance the stability of the catalyst.

附图说明Description of drawings

图1是实施例1制备得到的ZnO载体；Fig. 1 is the ZnO carrier that embodiment 1 prepares;

图2是实施例2制备得到的ZnO载体。Figure 2 is the ZnO carrier prepared in Example 2.

具体实施方式detailed description

实施例1Example 1

(1)室温条件下将5g摩尔比为1/3的Zn(NO3)2.6H2O和六次甲基四胺溶于100mL15wt％的乙二醇水溶液中。氮气气氛下，微波反应器中功率300W反应10min。降至室温，沉淀抽滤、用热去离子水洗涤至中性、90℃下干燥12h。合成ZnO-1载体。如图1所示，得到的催化剂中ZnO载体具有均一的纳米花状形貌；花瓣为棒状，花瓣长度为300～600nm；直径20～40nm。(1) 5 g of Zn(NO 3 ) 2 .6H 2 O and hexamethylenetetramine with a molar ratio of 1/3 were dissolved in 100 mL of 15 wt % ethylene glycol aqueous solution at room temperature. Under a nitrogen atmosphere, the reaction was carried out in a microwave reactor with a power of 300W for 10 minutes. Cool down to room temperature, filter the precipitate with suction, wash with hot deionized water until neutral, and dry at 90°C for 12 hours. Synthesis of ZnO-1 carrier. As shown in Figure 1, the ZnO carrier in the obtained catalyst has a uniform nano-flower shape; the petals are rod-shaped, and the length of the petals is 300-600 nm; the diameter is 20-40 nm.

(2)室温条件下将2.84gCu(NO3)2,5.1g(1)中得到的ZnO载体加入150mL去离子水中。600r/min下磁力搅拌加热至75℃,缓慢滴加0.1mol/LNa2CO3溶液至pH为9～10，进一步搅拌老化2h,沉淀抽滤、用热去离子水洗涤至中性、90℃下干燥12h，在400℃下于马弗炉中焙烧4h。合成Cu/ZnO-1催化剂。催化剂外观为褐色粉末，XRD测试结果表明Cu粒子平均粒径是10-25nm。(2) Add 2.84g of Cu(NO 3 ) 2 , 5.1g of the ZnO carrier obtained in (1) into 150mL of deionized water at room temperature. Stir magnetically at 600r/min and heat to 75°C, slowly add 0.1mol/L Na 2 CO 3 solution dropwise until the pH is 9-10, further stir and age for 2 hours, precipitate and filter, wash with hot deionized water until neutral, 90°C Drying at 400°C for 4 hours in a muffle furnace. Synthesis of Cu/ZnO-1 catalyst. The appearance of the catalyst is brown powder, and the XRD test result shows that the average particle size of Cu particles is 10-25nm.

实施例2Example 2

Zn(NO3)2.6H2O和六次甲基四胺的摩尔比为1/1，其余与实施例1相同。合成Cu/ZnO催化剂，命名为Cu/ZnO-2。如图2所示，得到的载体具有均一的纳米棒形貌；长度为2000～3000nm；直径10～30nm。催化剂外观为褐色粉末，XRD测试结果表明Cu粒子平均粒径同样在10-25nm之间。The molar ratio of Zn(NO 3 ) 2 .6H 2 O to hexamethylenetetramine was 1/1, and the rest were the same as in Example 1. The Cu/ZnO catalyst was synthesized and named as Cu/ZnO-2. As shown in Figure 2, the obtained carrier has a uniform nanorod shape; the length is 2000-3000nm; and the diameter is 10-30nm. The appearance of the catalyst is brown powder, and the XRD test results show that the average particle size of Cu particles is also between 10-25nm.

实施例3Example 3

Zn(NO3)2.6H2O和六次甲基四胺的摩尔比为1/0.5，其余与实施例1相同。合成Cu/ZnO催化剂，命名为Cu/ZnO-3。The molar ratio of Zn(NO 3 ) 2 .6H 2 O to hexamethylenetetramine was 1/0.5, and the rest were the same as in Example 1. The Cu/ZnO catalyst was synthesized and named as Cu/ZnO-3.

对比例1Comparative example 1

购买商业ZnO载体并用实施例1相同方法担载Cu，得到的催化剂命名为Cu/ZnO-4。Commercial ZnO supports were purchased and Cu was loaded in the same manner as in Example 1, and the obtained catalyst was named Cu/ZnO-4.

其中ZnO载体购自阿拉丁试剂(上海)有限公司，批号：Z111841，纯度：99.99％。透射电镜(TEM)结果表明此商业ZnO载体是无定形的颗粒，粒径在20-50nm。The ZnO carrier was purchased from Aladdin Reagent (Shanghai) Co., Ltd., batch number: Z111841, purity: 99.99%. Transmission electron microscopy (TEM) results show that the commercial ZnO support is amorphous particles with a particle size of 20-50nm.

应用例1Application example 1

称取0.15gCu/ZnO-1纳米催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:3000h-1，反应压力30bar。Weigh 0.15g Cu/ZnO-1 nano-catalyst and add it into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 3000h -1 , reaction pressure 30bar.

表1Table 1

应用例2Application example 2

称取0.15g15wt％Cu/ZnO-2纳米催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:3000h-1，反应压力30bar。Weigh 0.15g of 15wt% Cu/ZnO-2 nano-catalyst into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 3000h -1 , reaction pressure 30bar.

表2Table 2

应用例3Application example 3

称取0.15g15wt％Cu/ZnO-3纳米催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:3000h-1，反应压力30bar。Weigh 0.15g of 15wt% Cu/ZnO-3 nano-catalyst into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 3000h -1 , reaction pressure 30bar.

表3table 3

应用对比例4Application Comparative Example 4

称取0.15g15wt％Cu/ZnO-4商业催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:3000h-1，反应压力30bar。Weigh 0.15g of 15wt% Cu/ZnO-4 commercial catalyst and add it into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 3000h -1 , reaction pressure 30bar.

表4Table 4

应用例5Application example 5

称取0.15g15wt％Cu/ZnO-2催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:3000h-1，反应压力45bar。Weigh 0.15g of 15wt% Cu/ZnO-2 catalyst and add it into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 3000h -1 , reaction pressure 45bar.

表5table 5

应用例6Application example 6

称取0.15g15wt％Cu/ZnO-2催化剂加入到不锈钢反应管中，CO2/H2＝1/3(摩尔比)，GHSV:1500h-1，反应压力45bar。Weigh 0.15g of 15wt% Cu/ZnO-2 catalyst and add it into a stainless steel reaction tube, CO 2 /H 2 =1/3 (molar ratio), GHSV: 1500h -1 , reaction pressure 45bar.

表6Table 6

应用例7Application example 7

称取0.15g15wt％Cu/ZnO-2催化剂加入到不锈钢反应管中，CO2/H2＝1/1(摩尔比)，GHSV:3000h-1，反应压力45bar。Weigh 0.15g of 15wt% Cu/ZnO-2 catalyst and add it into a stainless steel reaction tube, CO 2 /H 2 =1/1 (molar ratio), GHSV: 3000h -1 , reaction pressure 45bar.

表7Table 7

反应活性及稳定性对比Reactivity and Stability Comparison

参见表2和表4，在270℃，30bar，CO2/H2＝1/3，GHSV:3000h-1反应条件下，担载型Cu/ZnO-2纳米催化剂上CO2转化率10.3％，甲醇选择性38％左右；而商业Cu/ZnO-4催化剂上同等反应条件下，CO2转化率只有5.1％，甲醇选择性也只有8.9％。See Table 2 and Table 4, under the reaction conditions of 270°C, 30bar, CO 2 /H 2 =1/3, GHSV: 3000h -1 , the conversion rate of CO 2 on the supported Cu/ZnO-2 nanocatalyst is 10.3%, The methanol selectivity is about 38%; while under the same reaction conditions on the commercial Cu/ZnO-4 catalyst, the CO2 conversion rate is only 5.1%, and the methanol selectivity is only 8.9%.

参见表2和表4，微波热解法合成的担载型Cu/ZnO-2催化剂，反应60h后，CO2转化率和甲醇选择性无显著降低。而商业Cu/ZnO-4催化剂反应60h后，CO2转化率和甲醇选择性均降低50％以上，催化剂失活严重。See Table 2 and Table 4, the supported Cu/ZnO-2 catalyst synthesized by microwave pyrolysis, after 60h of reaction, the CO2 conversion rate and methanol selectivity did not decrease significantly. While the commercial Cu/ZnO-4 catalyst reacted for 60 h, the CO2 conversion and methanol selectivity both decreased by more than 50%, and the catalyst deactivated seriously.

Claims (10)

1.一种Cu/ZnO催化剂，其特征在于：以铜为活性组分，ZnO为载体；催化剂中活性组分含量为10～15wt％；催化剂中ZnO载体具有均一的纳米花状和/或纳米棒形貌，铜粒子平均粒径为10～25nm。1. A Cu/ZnO catalyst is characterized in that: take copper as active component, and ZnO is carrier; Active component content is 10～15wt% in the catalyzer; ZnO carrier has uniform nano flower shape and/or nano Rod morphology, the average particle size of copper particles is 10-25nm. 2.如权利要求1所述Cu/ZnO催化剂的制备方法，其特征在于包括以下步骤：2. the preparation method of Cu/ZnO catalyst as claimed in claim 1, is characterized in that comprising the following steps: (1)ZnO载体制备：室温条件下将可溶性锌盐和六次甲基四胺按照摩尔比1:0.5～3溶于10～20wt％的乙二醇水溶液中；惰性气体气氛下，微波反应器中功率200～300W反应10～15min；降至室温，沉淀抽滤、洗涤、干燥；合成ZnO载体；(1) ZnO carrier preparation: under room temperature, soluble zinc salt and hexamethylenetetramine are dissolved in 10-20wt% ethylene glycol aqueous solution according to the molar ratio of 1:0.5-3; under inert gas atmosphere, microwave reactor Medium power 200~300W, react for 10~15min; cool down to room temperature, precipitate, filter, wash and dry; synthesize ZnO carrier; (2)负载活性金属铜：利用沉积沉淀法将活性金属铜担载在合成的ZnO载体上,其中可溶性铜盐和上述步骤(1)制备的ZnO载体质量比为1～4:2～11。(2) Loading active metal copper: The active metal copper is loaded on the synthesized ZnO carrier by deposition and precipitation method, wherein the mass ratio of soluble copper salt to the ZnO carrier prepared in the above step (1) is 1-4:2-11. 3.根据权利要求2所述Cu/ZnO催化剂的制备方法，其特征在于：步骤(2)中，室温条件下将可溶性铜盐和上述步骤(1)制备的ZnO载体溶于水中；搅拌加热至60～80℃,缓慢滴加0.1～0.3mol/L沉淀剂溶液至pH为9～10，进一步搅拌老化1～3h，沉淀抽滤、洗涤、干燥，在400～600℃下于马弗炉中焙烧4～8h；合成负载型Cu/ZnO催化剂。3. according to the preparation method of the described Cu/ZnO catalyst of claim 2, it is characterized in that: in step (2), the ZnO carrier prepared by soluble copper salt and above-mentioned step (1) is dissolved in water under room temperature condition; Stirring is heated to 60～80℃, slowly add 0.1～0.3mol/L precipitant solution dropwise until the pH is 9～10, further stir and age for 1～3h, the precipitate is suction filtered, washed and dried, and placed in a muffle furnace at 400～600℃ Calcination for 4-8 hours; synthesis of supported Cu/ZnO catalyst. 4.根据权利要求2所述Cu/ZnO催化剂的制备方法，其特征在于：步骤(1)中所述可溶性锌盐选自Zn(NO3)2.6H2O，ZnCl2。4. The preparation method of Cu/ZnO catalyst according to claim 2, characterized in that: the soluble zinc salt in step (1) is selected from Zn(NO 3 ) 2 .6H 2 O, ZnCl 2 . 5.根据权利要求2所述Cu/ZnO催化剂的制备方法，其特征在于：所述惰性气体为氮气，氦气，氩气。5. The preparation method of the Cu/ZnO catalyst according to claim 2, characterized in that: the inert gas is nitrogen, helium, argon. 6.根据权利要求2所述Cu/ZnO催化剂的制备方法，其特征在于：步骤(2)中所述可溶性铜盐选自Cu(NO3)2，CuSO4，CuCl2。6. The preparation method of Cu/ZnO catalyst according to claim 2, characterized in that: the soluble copper salt in step (2) is selected from Cu(NO 3 ) 2 , CuSO 4 , CuCl 2 . 7.根据权利要求2所述Cu/ZnO催化剂的制备方法，其特征在于:步骤(2)中所述沉淀剂选自Na2CO3，K2CO3。7. The preparation method of Cu/ZnO catalyst according to claim 2, characterized in that: the precipitating agent in step (2) is selected from Na 2 CO 3 , K 2 CO 3 . 8.根据权利要求1所述催化剂在CO2催化转化合成低碳醇反应中的应用。8. according to claim 1 described catalyzer is in CO Catalyzed conversion is synthesized the application in low-carbon alcohol reaction. 9.根据权利要求8所述应用，其特征在于：利用传统固定床反应器，将催化剂加入不锈钢反应管中，添加石英砂；反应温度250～270℃，反应压力30～45bar。9. The application according to claim 8, characterized in that: using a traditional fixed bed reactor, adding the catalyst into the stainless steel reaction tube and adding quartz sand; the reaction temperature is 250-270°C, and the reaction pressure is 30-45bar. 10.根据权利要求9所述应用，其特征在于：将0.1～0.5g催化剂加入不锈钢反应管中，添加石英砂至催化剂床层0.5～2.0cm；反应气为摩尔比为1/3的CO2/H2混合气，反应气流速为66～133mL/min，反应空速为2000～4000h-1。10. The application according to claim 9, characterized in that: add 0.1-0.5g of catalyst into the stainless steel reaction tube, add quartz sand to 0.5-2.0cm of the catalyst bed; the reaction gas is CO2 with a molar ratio of 1/3 /H 2 mixed gas, the reaction gas flow rate is 66-133mL/min, and the reaction space velocity is 2000-4000h -1 .
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