CN113559879B - Low-temperature synthesis method and application of corrosion-resistant high-entropy alloy nano-catalyst - Google Patents

Abstract

The invention discloses a low-temperature synthesis method and application of a corrosion-resistant high-entropy alloy nano catalyst, belonging to the technology in the fields of catalyst engineering and fine chemical engineering. The invention creatively applies the high-entropy alloy nano-catalyst which can still keep relatively stable in a severe service environment to the reaction. Synthesizing the corrosion-resistant high-entropy alloy nano-catalyst by adopting a liquid phase reduction method under mild conditions, wherein the reaction temperature is 60-140 ℃, the pressure is 0.5-1.0MPa, and the mass airspeed is 0.5-3h in a fixed bed reactor^‑1 The maleic anhydride is selectively hydrogenated to generate the succinic acid, the conversion rate can reach more than 95 percent, the selectivity can reach more than 98 percent, and the succinic acid has good stability. The catalyst has the advantages of simple preparation process, small obtained particle size, more exposed active sites, strong corrosion resistance, good catalytic property in a harsh reaction environment and wide application prospect.

Description

Translated fromChinese

一种耐腐蚀型高熵合金纳米催化剂低温合成方法及应用A low-temperature synthesis method and application of a corrosion-resistant high-entropy alloy nanocatalyst

技术领域technical field

本发明属于催化剂工程领域，涉及一种耐腐蚀型高熵合金纳米催化剂低温合成方法及应用。The invention belongs to the field of catalyst engineering, and relates to a low-temperature synthesis method and application of a corrosion-resistant high-entropy alloy nano-catalyst.

背景技术Background technique

随着科学技术的进步，人类生活水平的大幅度提升，物质基本上已经满足了人类所需，现在我们更想追求优美的环境、更想接触绿水青山，所以环保已经成了我们全人类所追求的。丁二酸作为当前生物可降解塑料聚丁二酸丁二醇酯的主要原料越来越得到科研工作者的关注，寻求采用环保的生产方法高产率、低成本地合成丁二酸已成为目前研究的热点。此外，丁二酸还广泛应用于表面活性剂、食品添加剂等。以水为溶剂对顺丁烯二酸酐选择性加氢生成丁二酸的方法有效避免了有机溶剂的使用，从而使得该工艺路径更加符合绿色化工的标准，且可以降低生产成本。从产物的分离上来说，一方面顺丁烯二酸酐水相加氢副产物较少，另一方面丁二酸与反应物顺丁烯二酸酐在水中的溶解度相差较大，所以后期可以通过降温结晶的方法得到较为纯净的丁二酸。由于该反应体系酸性较强，目前应用于该反应的催化剂虽可以达到很高的转化率及选择性，但普遍存在着催化剂寿命短、稳定性差的问题，所以对于寻找应用于酸性较强反应体系的催化剂尤其重要。With the advancement of science and technology, the living standards of human beings have been greatly improved, and the material has basically met the needs of human beings. Now we want to pursue a beautiful environment, and want to be in touch with green waters and green mountains. Therefore, environmental protection has become a priority for all of us. pursued. As the main raw material of the current biodegradable plastic polybutylene succinate, succinic acid has attracted more and more attention of scientific researchers, and it has become the current research to seek to use an environmentally friendly production method to synthesize succinic acid with high yield and low cost. hot spot. In addition, succinic acid is also widely used in surfactants, food additives, etc. The method for selectively hydrogenating maleic anhydride with water as a solvent to generate succinic acid effectively avoids the use of organic solvents, so that the process path is more in line with the standard of green chemical industry, and the production cost can be reduced. In terms of product separation, on the one hand, the water-phase hydrogenation of maleic anhydride has less by-products, and on the other hand, the solubility of succinic acid and the reactant maleic anhydride in water is quite different, so the later stage can be cooled by cooling. The method of crystallization obtains relatively pure succinic acid. Due to the strong acidity of the reaction system, although the catalysts currently used in this reaction can achieve high conversion and selectivity, there are generally problems of short catalyst life and poor stability. catalysts are particularly important.

高熵合金已被证明在电催化反应过程中表现优异，不仅可以降低贵金属的使用量，而且还具备高的稳定性以及高的活性。因此，将高熵合金应用于催化反应的研究越来越多。从高熵合金具备的特性来说仅仅把其应用于腐蚀性环境、温度不太高的电催化领域不能充分利用其高温稳定性，所以充分利用材料所具备的高温稳定及耐腐蚀的特性，将其用在热催化领域对热催化的发展及材料自身的发展极其重要。目前较为普遍的高熵合金的制备方法有真空电弧熔炼、碳热冲击法、多元醇法、脱合金法、纳米液滴介导电沉积法等制备方法。在目前这些存在的高熵合金合成的方法中，多是在>200℃的高温下进行合成的或是需要特殊的反应装置才可以进行的，低温实现高熵合金纳米催化剂的合成仍具备挑战。High-entropy alloys have been shown to perform well in electrocatalytic reactions, not only reducing the usage of noble metals, but also possessing high stability and high activity. Therefore, the application of high-entropy alloys in catalytic reactions is increasing. From the characteristics of high-entropy alloys, only applying them in corrosive environments and in the field of electrocatalysis where the temperature is not too high cannot make full use of their high-temperature stability. Its use in the field of thermocatalysis is extremely important for the development of thermocatalysis and the development of the material itself. At present, the more common preparation methods of high-entropy alloys include vacuum arc melting, carbon thermal shock method, polyol method, dealloying method, nano-droplet-mediated electro-deposition method and other preparation methods. Among the existing high-entropy alloy synthesis methods, most of them are synthesized at a high temperature of >200 °C or require special reaction equipment. It is still challenging to realize the synthesis of high-entropy alloy nanocatalysts at low temperature.

中国专利CN106861702A公开了一种用于顺丁烯二酸酐水相加氢的碳包覆镍铜的Cu-Ni/Al₂O₃@C催化剂，虽然该催化剂在顺丁烯二酸酐加氢中取得了较好的转化率及选择性，但就其对催化过程的叙述来看，催化剂的积碳问题会很严重，并没有解决目前顺丁烯二酸酐水相加氢中催化剂寿命短的问题，另一方面从催化剂的制备来说，其处理步骤复杂，经过多次焙烧，催化剂的粒子较大，并不有利于催化反应的进行。Chinese patent CN106861702A discloses a carbon-coated nickel-copper Cu-Ni/Al₂ O₃ @C catalyst for the aqueous hydrogenation of maleic anhydride, although the catalyst was obtained in the hydrogenation of maleic anhydride However, according to its description of the catalytic process, the carbon deposition problem of the catalyst will be very serious, and it does not solve the problem of short catalyst life in the current aqueous hydrogenation of maleic anhydride. On the other hand, in terms of catalyst preparation, the processing steps are complicated, and after multiple calcinations, the particles of the catalyst are larger, which is not conducive to the progress of the catalytic reaction.

中国专利CN110339850A公开了一种用于析氢反应的Fe-Co-Ni-P-C系高熵合金电催化剂的制备方法，将Fe、Co、Ni金属单质和C粉、P粉进行配料，用真空电弧熔炼炉熔炼，然后在高真空条件下将熔融态合金喷射到高速旋转的铜辊上，通过铜辊的导热将熔融态合金快速冷却，得到用于催化析氢的电催化剂。该合成方法对合成装置以及合成技术要求较高，且该过程较为耗能，步骤繁琐过多。Chinese patent CN110339850A discloses a preparation method of Fe-Co-Ni-P-C series high-entropy alloy electrocatalyst for hydrogen evolution reaction. The molten alloy is smelted in a furnace, and then the molten alloy is sprayed onto a high-speed rotating copper roll under high vacuum conditions, and the molten alloy is rapidly cooled by the heat conduction of the copper roll to obtain an electrocatalyst for catalyzing hydrogen evolution. The synthesis method has high requirements on the synthesis device and synthesis technology, and the process is relatively energy-intensive and the steps are too complicated.

中国专利CN112475315A公开了一种普适性制备高熵合金纳米颗粒的方法，分别将两种以上的等原子比或近等原子比的金属有机前驱体以及一定质量的载体或载体和有机配体溶解或分散在一定体积的氯仿、丙酮、水、乙醇等溶剂中，然后将两种分散液体进行超声处理，将用于分散的液体挥发掉得到前驱体，之后在真空或还原性气氛中，将前驱体置于管式炉中，升温至所需的还原温度，保持一定时间，金属有机前驱体热解还原得到负载型高熵合金纳米颗粒。该方法仍需采用高温处理，制备条件苛刻。Chinese patent CN112475315A discloses a universal method for preparing high-entropy alloy nanoparticles, respectively dissolving two or more metal-organic precursors of equal atomic ratio or nearly equal atomic ratio and a certain quality of carrier or carrier and organic ligand. Or dispersed in a certain volume of chloroform, acetone, water, ethanol and other solvents, and then ultrasonically treated the two dispersion liquids, volatilize the liquid used for dispersion to obtain the precursor, and then in a vacuum or reducing atmosphere, the precursor is The body is placed in a tube furnace, heated to a desired reduction temperature, and kept for a certain period of time, and the metal-organic precursor is pyrolyzed and reduced to obtain loaded high-entropy alloy nanoparticles. This method still requires high temperature treatment and harsh preparation conditions.

发明内容SUMMARY OF THE INVENTION

本发明提供了一种耐腐蚀型高熵合金纳米催化剂低温合成方法及顺丁烯二酸酐水相加氢应用。针对目前顺丁烯二酸酐水相加氢催化剂普遍存在稳定性差的问题，本发明开创性的把在严峻的服役环境(高温、腐蚀和高电化学势)中仍能保持相对稳定的高熵合金材料应用于此反应，并且针对目前合成高熵合金需要在高温亦或是在殊装置下合成的弊端提供一种低温简单的解决方法，该方法利用液相共还原的原理得到了催化性能较为优异的高熵合金纳米催化剂。与其他制备方法相比，该方法具有以下优势，其一不需要特殊的装置；其二，合成温度较低，30℃至75℃，避免了合成过程中催化剂粒子的团聚长大等问题；其三，所合成的高熵合金纳米催化剂在顺丁烯二酸酐水相加氢反应中表现出高的催化活性和对丁二酸的高选择性以及持久稳定性。The invention provides a low-temperature synthesis method of a corrosion-resistant high-entropy alloy nano-catalyst and its application in the aqueous hydrogenation of maleic anhydride. In view of the general problem of poor stability of the current maleic anhydride aqueous hydrogenation catalysts, the present invention pioneers a high-entropy alloy that can remain relatively stable in severe service environments (high temperature, corrosion and high electrochemical potential). The material is used in this reaction, and a low-temperature and simple solution is provided for the disadvantage that the current synthesis of high-entropy alloys needs to be synthesized at high temperature or in a special device. This method uses the principle of liquid phase co-reduction to obtain excellent catalytic performance. high-entropy alloy nanocatalysts. Compared with other preparation methods, this method has the following advantages. First, no special equipment is required; second, the synthesis temperature is low, ranging from 30 ° C to 75 ° C, which avoids problems such as agglomeration and growth of catalyst particles during the synthesis process; Third, the synthesized high-entropy alloy nanocatalysts exhibited high catalytic activity, high selectivity to succinic acid, and long-lasting stability in the aqueous hydrogenation of maleic anhydride.

本发明的技术方案：Technical scheme of the present invention:

一种耐腐蚀型高熵合金纳米催化剂低温合成方法，步骤如下：A low-temperature synthesis method of a corrosion-resistant high-entropy alloy nano-catalyst, the steps are as follows:

利用液相共还原法，以萘锂为还原剂、等摩尔量金属的乙酰丙酮络合物为前驱体、金属氧化物或碳材料为载体，在四氢呋喃溶液中，控制还原剂与前驱体摩尔比为1.3-2.0：1，温度30℃-75℃、还原3-7h，经洗涤、离心、干燥后获得负载量为0.5-5wt.％的耐腐蚀型高熵合金纳米催化剂。Using the liquid phase co-reduction method, using lithium naphthalene as reducing agent, acetylacetone complex of equimolar amount of metal as precursor, metal oxide or carbon material as carrier, in tetrahydrofuran solution, the molar ratio of reducing agent and precursor is controlled. The ratio is 1.3-2.0:1, the temperature is 30°C-75°C, the reduction is 3-7h, and the corrosion-resistant high-entropy alloy nanocatalyst with a loading of 0.5-5wt.% is obtained after washing, centrifugation and drying.

所述的耐腐蚀型高熵合金纳米催化剂为：PtFeCoNiCu/CNTs、PdFeCoNiCu/CNTs、RuFeCoNiCu/C、PtFeCoNiCu/ZrO₂、PdFeCoNiCu/ZrO₂、RuFeCoNiCu/ZrO₂、PtFeCoNiCu/CeO₂、PdFeCoNiCu/CeO₂、RuFeCoNiCu/CeO₂中的一种，其中高熵合金每种原子所占的比例为1:1:1:1:1。The corrosion-resistant high-entropy alloy nano-catalysts are: PtFeCoNiCu/CNTs, PdFeCoNiCu/CNTs, RuFeCoNiCu/C, PtFeCoNiCu/ZrO₂ , PdFeCoNiCu/ZrO₂ , RuFeCoNiCu/ZrO₂ , PtFeCoNiCu/CeO₂ , PdFeCoNiCu/CeO₂ , One of RuFeCoNiCu/CeO₂ , in which the ratio of each atom of the high-entropy alloy is 1:1:1:1:1.

针对底物浓度为5-20wt.％的顺酐水溶液，在固定床反应器中反应温度为60-140℃、反应的压力为0.5-1.0MPa、质量空速0.5-3h^-1下，氢气与顺酐的摩尔比为200：1，采用所制备的高熵合金纳米催化剂选择性催化顺酐水相加氢制备丁二酸。For an aqueous solution of maleic anhydride with a substrate concentration of 5-20 wt.%, in a fixed-bed reactor, the reaction temperature is 60-140 °C, the reaction pressure is 0.5-1.0 MPa, and the mass space velocity is 0.5-3 h^-1 . The molar ratio of maleic anhydride is 200:1, and the prepared high-entropy alloy nano-catalyst is used to selectively catalyze the aqueous hydrogenation of maleic anhydride to prepare succinic acid.

该耐腐蚀型高熵合金纳米催化剂还适用于不饱和有机酸的选择性加氢，如丙烯酸选择性加氢生成丙酸。The corrosion-resistant high-entropy alloy nanocatalyst is also suitable for the selective hydrogenation of unsaturated organic acids, such as the selective hydrogenation of acrylic acid to generate propionic acid.

本发明的有益效果：制备工艺简单，得到的粒径较小，活性位点暴露多，在用于顺丁烯二酸酐水相加氢时不仅能够保证高的转化率及选择性还能够有很好的稳定性。The beneficial effects of the invention are as follows: the preparation process is simple, the obtained particle size is small, the active sites are exposed more, and when it is used for the aqueous hydrogenation of maleic anhydride, it can not only ensure high conversion rate and selectivity, but also have high good stability.

附图说明Description of drawings

图1是采用低温还原法制备出来的PtFeCoNiCu/CNTs的负载型催化剂的XRD图。Figure 1 is the XRD pattern of the supported catalyst of PtFeCoNiCu/CNTs prepared by the low temperature reduction method.

图2是PtFeCoNiCu/CNTs催化剂对顺丁烯二酸酐水相加氢的稳定性测试数据。Figure 2 shows the stability test data of PtFeCoNiCu/CNTs catalyst for the hydrogenation of maleic anhydride in water.

具体实施方式Detailed ways

下面将通过实施案例来详述本发明，下面表述的实施案例是示例性的，仅用于解释本发明，但本发明并不局限于这些实施例。The present invention will be described in detail below through examples of implementation. The examples of implementation described below are exemplary and are only used to explain the present invention, but the present invention is not limited to these examples.

实施例1 PtFeCoNiCu/CNTs催化剂的制备Example 1 Preparation of PtFeCoNiCu/CNTs catalyst

取0.7434g的萘、0.0352g的Li及0.8642g的碳纳米管依次加入到60mL的四氢呋喃中，搅拌过夜，在碳纳米管上得到分散较为均匀的还原位点，取0.0811g(0.2mmol)的乙酰丙酮铂、0.0721g的乙酰丙酮铁、0.0530g的乙酰丙酮钴、0.0541g的乙酰丙酮镍、0.0540g的乙酰丙酮铜加入20mL四氢呋喃中，搅拌使其溶解，得到金属盐溶液，将搅拌过夜的碳纳米管加热至30℃，在剧烈搅拌下快速加入金属盐前驱体溶液中，反应7h，后经洗涤、离心、干燥得到黑色固体粉末，即为负载量为5wt.％的PtFeCoNiCu/CNTs催化剂。Take 0.7434g of naphthalene, 0.0352g of Li and 0.8642g of carbon nanotubes and add them to 60mL of tetrahydrofuran in turn, stir overnight to obtain a relatively uniformly dispersed reduction site on the carbon nanotubes, take 0.0811g (0.2mmol) of Platinum acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate, and 0.0540g of copper acetylacetonate were added to 20 mL of tetrahydrofuran, and stirred to dissolve to obtain a metal salt solution. The carbon nanotubes were heated to 30 °C, rapidly added to the metal salt precursor solution under vigorous stirring, reacted for 7 h, and then washed, centrifuged, and dried to obtain a black solid powder, which was a PtFeCoNiCu/CNTs catalyst with a loading of 5 wt.%.

实施例2 PtFeCoNiCu/CNTs催化剂的制备Example 2 Preparation of PtFeCoNiCu/CNTs catalyst

取0.7434g的萘、0.0352g的Li及8.642g的碳纳米管依次加入到60mL的四氢呋喃中，搅拌过夜，在碳纳米管上得到分散较为均匀的还原位点，取0.0811g(0.2mmol)的乙酰丙酮铂、0.0721g的乙酰丙酮铁、0.0530g的乙酰丙酮钴、0.0541g的乙酰丙酮镍、0.0540g的乙酰丙酮铜加入20mL四氢呋喃中，搅拌使其溶解，得到金属盐溶液，将搅拌过夜的碳纳米管加热至30℃，在剧烈搅拌下快速加入金属盐前驱体溶液中，反应3h，后经洗涤、离心、干燥得到黑色固体粉末，即为负载量为0.5wt.％的PtFeCoNiCu/CNTs催化剂。Take 0.7434g of naphthalene, 0.0352g of Li and 8.642g of carbon nanotubes and add them to 60mL of tetrahydrofuran in turn, stir overnight to obtain a relatively uniformly dispersed reduction site on the carbon nanotubes, take 0.0811g (0.2mmol) of Platinum acetylacetonate, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate, and 0.0540g of copper acetylacetonate were added to 20 mL of tetrahydrofuran, and stirred to dissolve to obtain a metal salt solution. The carbon nanotubes were heated to 30°C, rapidly added to the metal salt precursor solution under vigorous stirring, reacted for 3 hours, and then washed, centrifuged and dried to obtain black solid powder, which was a PtFeCoNiCu/CNTs catalyst with a loading of 0.5 wt.% .

实施例3 PdFeCoNiCu/ZrO₂催化剂的制备Example 3 Preparation of PdFeCoNiCu/ZrO₂ Catalyst

取0.7434g的萘、0.0352g的Li、0.8642g的氧化锆依次加入到60mL的四氢呋喃中，搅拌过夜，在氧化锆上得到分散较为均匀的还原位点，取0.0609g(0.2mmol)的乙酰丙酮钯、0.0721g的乙酰丙酮铁、0.0530g的乙酰丙酮钴、0.0541g的乙酰丙酮镍、0.0540g的乙酰丙酮铜加入20mL四氢呋喃中，搅拌使其溶解，得到金属盐溶液，将搅拌过夜的氧化锆加热至75℃，在剧烈搅拌下快速加入金属盐前驱体溶液中，反应3h,后经离心、干燥，得到负载量为5wt.％的PdFeCoNiCu/ZrO₂催化剂。Take 0.7434g of naphthalene, 0.0352g of Li, and 0.8642g of zirconium oxide and add them to 60mL of tetrahydrofuran in turn, stir overnight to obtain a relatively uniformly dispersed reduction site on the zirconium oxide, take 0.0609g (0.2mmol) of acetylacetone Palladium, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate, and 0.0540g of copper acetylacetonate were added to 20 mL of tetrahydrofuran, and stirred to dissolve to obtain a metal salt solution. It was heated to 75°C, rapidly added to the metal salt precursor solution under vigorous stirring, reacted for 3 h, and then centrifuged and dried to obtain a PdFeCoNiCu/ZrO₂ catalyst with a loading of 5 wt.%.

实施例4 RuFeCoNiCu/CeO₂催化剂的制备Example 4 Preparation of RuFeCoNiCu/CeO₂ catalyst

取0.7434g的萘、0.0352g的Li及0.8642g的氧化铈依次加入到60mL的四氢呋喃中，搅拌过夜，在氧化铈上得到分散较为均匀的还原位点，取0.0797g(0.2mmol)的乙酰丙酮钌、0.0721g的乙酰丙酮铁、0.0530g的乙酰丙酮钴、0.0541g的乙酰丙酮镍、0.0540g的乙酰丙酮铜加入20mL四氢呋喃中，搅拌使其溶解，得到金属盐溶液，将搅拌过夜的氧化铈加热至62℃，在剧烈搅拌下快速加入金属盐前驱体溶液中，反应7h，后经洗涤、离心、干燥得到固体粉末，即为负载量为5wt.％的RuFeCoNiCu/CeO₂催化剂。Take 0.7434g of naphthalene, 0.0352g of Li and 0.8642g of cerium oxide and add them to 60mL of tetrahydrofuran in turn, stir overnight to obtain a relatively evenly dispersed reduction site on the cerium oxide, take 0.0797g (0.2mmol) of acetylacetone Ruthenium, 0.0721g of iron acetylacetonate, 0.0530g of cobalt acetylacetonate, 0.0541g of nickel acetylacetonate, and 0.0540g of copper acetylacetonate were added to 20mL of tetrahydrofuran, and stirred to dissolve to obtain a metal salt solution. It was heated to 62°C, rapidly added to the metal salt precursor solution under vigorous stirring, reacted for 7 hours, and then washed, centrifuged, and dried to obtain a solid powder, which was a RuFeCoNiCu/CeO₂ catalyst with a loading of 5 wt.%.

实施例5在固定床中PtFeCoNiCu/CNTs催化剂对顺丁烯二酸酐水相加氢。Example 5 Hydrogenation of aqueous maleic anhydride over PtFeCoNiCu/CNTs catalyst in a fixed bed.

以5wt.％的顺丁烯二酸酐进行选择性加氢反应，以水为溶剂，反应在固定床中进行，首先顺丁烯二酸酐在水相中水解为顺丁烯二酸。反应条件为：催化剂PtFeCoNiCu/CNTs：0.2g，反应压力为1MPa,反应温度为80℃，氢气与顺丁烯二酸酐的摩尔比为200：1，质量空速为3h^-1，底物通过高效液相色谱进行分析，转化率达95％，选择性99％以上。The selective hydrogenation reaction is carried out with 5 wt. % maleic anhydride, and water is used as a solvent, and the reaction is carried out in a fixed bed. First, the maleic anhydride is hydrolyzed into maleic acid in the water phase. The reaction conditions are: catalyst PtFeCoNiCu/CNTs: 0.2g, reaction pressure is 1MPa, reaction temperature is 80℃, the molar ratio of hydrogen to maleic anhydride is 200:1, the mass space velocity is 3h^-1 , the substrate passes through efficiently Analyzed by liquid chromatography, the conversion rate is 95%, and the selectivity is more than 99%.

实施例6在固定床中RuFeCoNiCu/CeO₂催化剂对顺丁烯二酸酐水相加氢。Example 6 Aqueous hydrogenation of maleic anhydride with_RuFeCoNiCu /CeO2 catalyst in a fixed bed.

以20wt.％的顺丁烯二酸酐进行选择性加氢反应，以水为溶剂，反应在固定床中进行。反应条件为：催化剂PtFeCoNiCu/CNTs：0.2g，反应压力为1MPa，在质量空速为0.5h^-1，氢气与顺丁烯二酸酐的摩尔比为200：1，在140℃范围内进行反应，产物通过高效液相色谱进行分析，转化率达99％，对丁二酸的选择性为96％。The selective hydrogenation reaction was carried out with 20 wt.% maleic anhydride, and the reaction was carried out in a fixed bed with water as a solvent. The reaction conditions are: catalyst PtFeCoNiCu/CNTs: 0.2g, reaction pressure is 1MPa, mass space velocity is 0.5h^-1 , the molar ratio of hydrogen to maleic anhydride is 200:1, and the reaction is carried out in the range of 140°C, The product was analyzed by high performance liquid chromatography, the conversion rate was 99%, and the selectivity to succinic acid was 96%.

实施例7在固定床中PtFeCoNiCu/CNTs催化剂对顺丁烯二酸酐水相加氢。Example 7 Hydrogenation of aqueous maleic anhydride over PtFeCoNiCu/CNTs catalyst in a fixed bed.

以5wt.％的顺丁烯二酸酐进行选择性加氢反应，以水为溶剂，反应在固定床中进行。反应条件为：催化剂PtFeCoNiCu/CNTs：0.2g，反应压力为1MPa,在质量空速为0.75h^-1，80℃，氢气与顺丁烯二酸酐的摩尔比为200：1，在此条件下进行稳定性测试100h。产物通过高效液相色谱进行分析，发现顺丁烯二酸酐的转化率维持在96％以上，对丁二酸的选择性维持在98％以上。反应结果如图2。The selective hydrogenation reaction was carried out with 5 wt.% maleic anhydride, and the reaction was carried out in a fixed bed with water as a solvent. The reaction conditions are: catalyst PtFeCoNiCu/CNTs: 0.2g, reaction pressure is 1MPa, mass space velocity is 0.75h^-1 , 80°C, the molar ratio of hydrogen to maleic anhydride is 200:1, under these conditions Stability test 100h. The product was analyzed by high performance liquid chromatography, and it was found that the conversion rate of maleic anhydride was maintained above 96%, and the selectivity to succinic acid was maintained above 98%. The reaction results are shown in Figure 2.

实施例8在固定床中PdFeCoNiCu/ZrO₂催化剂对丙烯酸水相加氢。Example 8 Hydrogenation of aqueous acrylic acid over_PdFeCoNiCu /ZrO2 catalyst in a fixed bed.

以20wt.％的丙烯酸进行选择性加氢反应，以水为溶剂，反应在固定床中进行。反应条件为：催化剂PdFeCoNiCu/ZrO₂：0.2g，反应压力为1MPa，反应温度为140℃，氢气与丙烯酸的摩尔比为200：1，质量空速为3h^-1，底物通过高效液相色谱进行分析，转化率最高可达98％，丙酸选择性99％以上。The selective hydrogenation reaction was carried out with 20 wt.% acrylic acid and water as solvent, and the reaction was carried out in a fixed bed. The reaction conditions are: catalyst PdFeCoNiCu/ZrO₂ : 0.2g, reaction pressure 1MPa, reaction temperature 140°C, molar ratio of hydrogen to acrylic acid 200:1, mass space velocity 3h^-1 , and the substrate is passed through high performance liquid chromatography According to the analysis, the conversion rate can reach up to 98%, and the selectivity of propionic acid is more than 99%.

Claims (4)

Translated fromChinese

1.一种耐腐蚀型高熵合金纳米催化剂低温合成方法，其特征在于，步骤如下：1. a corrosion-resistant high-entropy alloy nano-catalyst low-temperature synthesis method, is characterized in that, step is as follows:利用液相共还原法，以萘锂为还原剂、等摩尔量金属的乙酰丙酮络合物为前驱体、金属氧化物或碳材料为载体，在四氢呋喃溶液中，控制还原剂与前驱体摩尔比为1.3-2.0：1，温度30^oC-75^oC、还原3-7 h，经洗涤、离心、干燥后获得负载量为0.5-5 wt.%的耐腐蚀型高熵合金纳米催化剂。Using the liquid phase co-reduction method, using lithium naphthalene as the reducing agent, acetylacetone complexes of equimolar metals as the precursor, metal oxides or carbon materials as the carrier, in a tetrahydrofuran solution, the molar ratio of the reducing agent and the precursor is controlled. It is 1.3-2.0:1, the temperature is 30^o C-75^o C, and the reduction is 3-7 h. After washing, centrifugation, and drying, a corrosion-resistant high-entropy alloy nanocatalyst with a loading of 0.5-5 wt.% is obtained.2.根据权利要求1所述的低温合成方法，其特征在于，所述的耐腐蚀型高熵合金纳米催化剂为：PtFeCoNiCu/CNTs、PdFeCoNiCu/CNTs、RuFeCoNiCu/C、PtFeCoNiCu/ZrO₂、PdFeCoNiCu/ZrO₂、RuFeCoNiCu/ZrO₂、PtFeCoNiCu/CeO₂、PdFeCoNiCu/CeO₂、RuFeCoNiCu/CeO₂中的一种，其中高熵合金每种原子所占的比例为1:1:1:1:1。2. The low-temperature synthesis method according to claim 1, wherein the corrosion-resistant high-entropy alloy nanocatalyst is: PtFeCoNiCu/CNTs, PdFeCoNiCu/CNTs, RuFeCoNiCu/C, PtFeCoNiCu/ZrO₂ , PdFeCoNiCu/ZrO_2. One of RuFeCoNiCu/ZrO₂ , PtFeCoNiCu/CeO₂ , PdFeCoNiCu/CeO₂ , RuFeCoNiCu/CeO₂ , wherein the ratio of each atom of the high-entropy alloy is 1:1:1:1:1.3.权利要求2所述的低温合成方法合成的耐腐蚀型高熵合金纳米催化剂的应用，其特征在于，针对底物浓度为5-20 wt.%的顺酐水溶液，在固定床反应器中反应温度为60-140℃、反应的压力为0.5-1.0 MPa、质量空速0.5-3 h^-1下，氢气与顺酐的摩尔比为200：1，采用所制备的高熵合金纳米催化剂选择性催化顺酐水相加氢制备丁二酸。3. the application of the corrosion-resistant high-entropy alloy nano-catalyst synthesized by the low-temperature synthesis method of claim 2, is characterized in that, for substrate concentration, be the maleic anhydride aqueous solution of 5-20 wt.%, in the fixed-bed reactor The reaction temperature is 60-140 °C, the reaction pressure is 0.5-1.0 MPa, the mass space velocity is 0.5-3 h^-1 , the molar ratio of hydrogen to maleic anhydride is 200:1, and the prepared high-entropy alloy nanocatalyst is selected as Catalytic aqueous hydrogenation of maleic anhydride to produce succinic acid.4.权利要求2所述的低温合成方法合成的耐腐蚀型高熵合金纳米催化剂在不饱和有机酸选择性加氢中的应用。4. Application of the corrosion-resistant high-entropy alloy nano-catalyst synthesized by the low-temperature synthesis method of claim 2 in the selective hydrogenation of unsaturated organic acids.

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