WO2023082321A1 - Platinum/molybdenum catalytic material for dehydrogenation, and preparation method therefor and use thereof - Google Patents

Platinum/molybdenum catalytic material for dehydrogenation, and preparation method therefor and use thereof Download PDF

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WO2023082321A1
WO2023082321A1 PCT/CN2021/132234 CN2021132234W WO2023082321A1 WO 2023082321 A1 WO2023082321 A1 WO 2023082321A1 CN 2021132234 W CN2021132234 W CN 2021132234W WO 2023082321 A1 WO2023082321 A1 WO 2023082321A1
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platinum
molybdenum
dehydrogenation
catalytic material
preparation
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陈琪
尹中南
刘冬妮
周子兵
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苏州金宏气体股份有限公司
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • the invention relates to the technical field of liquid hydrogen storage catalytic dehydrogenation, in particular to a platinum/molybdenum dehydrogenation catalytic material, a preparation method and an application thereof.
  • Organic hydrogen storage liquid is one of the most likely solutions to the hydrogen storage problem, but its hydrogen absorption and desorption kinetics are poor.
  • it is basically necessary to use noble metal catalysts to catalyze the hydrogen absorption and desorption process, and the hydrogenation process and dehydrogenation process often require The use of different precious metals leads to high cost and is difficult for practical application.
  • dehydrogenation is a strong endothermic and highly reversible reaction.
  • high temperature is beneficial to the dehydrogenation reaction, but hydrogen storage materials at high temperatures may undergo side reactions such as cracking and carbon deposition.
  • the catalyst is poisoned.
  • the purpose of the present invention is to provide a platinum/molybdenum dehydrogenation catalytic material, a preparation method and its application. By optimizing the combination of active molding, the dehydrogenation efficiency is effectively improved, and the catalytic dehydrogenation of liquid hydrogen storage materials is greatly improved. ability.
  • embodiments of the present invention provide a platinum/molybdenum dehydrogenation catalytic material, including a carrier and a catalytic composition formed on the carrier, the catalytic composition accounts for 0.75-1.5% of the total mass of the catalytic material, and the The catalytic composition includes platinum and molybdenum.
  • the mass ratio of platinum element to molybdenum element in the catalytic composition is 1:(0.5-2).
  • the platinum element is at least derived from any one of the following: Pt(NO 3 ) 4 , H 2 PtCl 6 .
  • the molybdenum element is at least derived from any of the following: molybdic acid and molybdate.
  • the carrier is selected from any one of the following: alumina, TiO 2 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , CoO, NiO, CuO and ZrO 2 .
  • the preparation method of platinum/molybdenum dehydrogenation catalytic material is characterized in that it includes the following steps: preparing a mixed solution containing platinum source and molybdenum source; Solution, fully soaked and dried, and then sintered under oxygen-poor conditions.
  • the drying is at 80-100 degrees for 2-4 hours.
  • the oxygen-depleted conditions are hydrogen conditions.
  • the sintering is carried out under oxygen-poor conditions, and the temperature is raised to 250-350 degrees, and kept for 2-6 hours.
  • the aforementioned platinum/molybdenum dehydrogenation catalytic material is used in liquid hydrogen storage technology.
  • the platinum/molybdenum dehydrogenation catalytic material according to the embodiment of the present invention has simple preparation, stable composition, simple composition of matrix and active components, high activity and anti-toxicity, and can effectively improve catalytic performance. dehydrogenation efficiency.
  • Fig. 1 is a comparison chart of dehydrogenation performance of catalytic materials with different compositions according to an embodiment of the present invention.
  • Fig. 2 is a comparison chart of dehydrogenation performance of catalytic materials with different supports according to an embodiment of the present invention.
  • the physical properties of the carrier are all in the same form: spherical porous particles with a particle size of 3 mm and a specific surface area of 5 square meters per gram.
  • the production process of the dehydrogenation catalyst in the prior art is complicated, the energy consumption is high, the cost is high, and the active components of the catalyst and the carrier are all components It is complex and requires a large amount of expensive materials, which greatly increases the application cost of catalytic materials.
  • the platinum/molybdenum dehydrogenation catalytic material according to the preferred embodiment of the present invention has certain adaptability to various supports.
  • it also reflects a certain performance selectivity, which may be related to The atomic number of metal elements has a certain correlation.

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Abstract

A platinum/molybdenum catalytic material for dehydrogenation, and a preparation method therefor and the use thereof. The catalytic material comprises a carrier and a catalytic composition formed on the carrier, wherein the catalytic composition accounts for 0.75-1.5% of the total mass of the catalytic material, and the catalytic composition comprises platinum and molybdenum. According to the catalytic material, by means of optimizing and combining active ingredients, the dehydrogenation efficiency is effectively improved.

Description

铂/钼脱氢催化材料、制备方法及其应用Platinum/molybdenum dehydrogenation catalytic material, preparation method and application thereof
本发明要求2021年11月11日向中国专利局提交的、申请号为202111334685X、发明名称为“铂钼脱氢催化材料、制备方法及其应用”的中国专利申请的优先权，该申请的全部内容通过引用结合在本文中。The present invention claims the priority of the Chinese patent application with the application number 202111334685X and the title of the invention "platinum molybdenum dehydrogenation catalytic material, preparation method and application" submitted to the China Patent Office on November 11, 2021, and the entire content of the application Incorporated herein by reference.
技术领域technical field
本发明关于液体储氢催化脱氢技术领域，特别是关于一种铂/钼脱氢催化材料、制备方法及其应用。The invention relates to the technical field of liquid hydrogen storage catalytic dehydrogenation, in particular to a platinum/molybdenum dehydrogenation catalytic material, a preparation method and an application thereof.
背景技术Background technique
氢能源清洁无污染、高热值等一系列的优势使其在近几十年来备受期待，被许多人认为是解决能源问题、发展低碳经济不可或缺的一部分。尽管氢能源正在蓬勃发展，但是制氢、储氢和燃料电池三个方面的关键问题并没有得到很好的解决。特别是作为起到氢气制备与应用之间桥梁作用的储氢，还未有特别成熟的可广泛应用的储氢方式。目前的车载储氢方式还是利用物理型高压储氢罐储氢的方式，在能量效率、体积储氢量、安全性等方面还有许多不足之处。因此，高效储氢材料的缺乏可以说是氢能源发展中一个亟待解决的瓶颈问题。A series of advantages such as clean, pollution-free and high calorific value of hydrogen energy have made it highly anticipated in recent decades, and are considered by many people to be an indispensable part of solving energy problems and developing a low-carbon economy. Although hydrogen energy is developing vigorously, the key issues in the three aspects of hydrogen production, hydrogen storage and fuel cells have not been well resolved. Especially for hydrogen storage, which acts as a bridge between hydrogen production and application, there is no particularly mature hydrogen storage method that can be widely used. The current on-board hydrogen storage method still uses physical high-pressure hydrogen storage tanks to store hydrogen, which still has many shortcomings in terms of energy efficiency, volumetric hydrogen storage capacity, and safety. Therefore, the lack of efficient hydrogen storage materials can be said to be a bottleneck problem that needs to be solved urgently in the development of hydrogen energy.
有机储氢液体是最有可能解决储氢问题的方案之一，但是其吸放氢动力学差，目前基本都需要使用贵金属催化剂催化其吸放氢过程，而且加氢过程和脱氢过程常常需要使用不同的贵金属，导致使用成本太高，难以实际应用。在现有的技术条件下，脱氢是一个强吸热、高度可逆的反应，虽然在一个方面讲，高温有利于脱氢反应进行，但是高温下储氢材料以发生裂解、积碳等副反应而使催化剂中毒，同时目前的催化剂大多组成复杂并且一般情况下需要多种催化剂与特定的载体材料，特别是特定的多孔载体材料相配合才能有效起到一定的催化效能，这极大地影响了应用成本和催化材料的大规模生产。比如CN201410539305多孔三氧化钼及其制备方法、加氢催化剂及脱氢催化剂，就存在效率低、催化剂组成和生产复杂，对催化剂的组分配合要求严格等的问题。Organic hydrogen storage liquid is one of the most likely solutions to the hydrogen storage problem, but its hydrogen absorption and desorption kinetics are poor. At present, it is basically necessary to use noble metal catalysts to catalyze the hydrogen absorption and desorption process, and the hydrogenation process and dehydrogenation process often require The use of different precious metals leads to high cost and is difficult for practical application. Under the existing technical conditions, dehydrogenation is a strong endothermic and highly reversible reaction. Although in one respect, high temperature is beneficial to the dehydrogenation reaction, but hydrogen storage materials at high temperatures may undergo side reactions such as cracking and carbon deposition. However, the catalyst is poisoned. At the same time, most of the current catalysts are complex in composition and generally require a variety of catalysts to cooperate with specific carrier materials, especially specific porous carrier materials, to effectively achieve a certain catalytic performance, which greatly affects the application. Cost and large-scale production of catalytic materials. For example, CN201410539305 porous molybdenum trioxide and its preparation method, hydrogenation catalyst and dehydrogenation catalyst have problems such as low efficiency, complex catalyst composition and production, and strict requirements on the composition of the catalyst.
基于对新能源载具的应用需求，储氢装置的载氢脱氢的循环效率和速度，大大限制 了有机储氢液体在氢燃料电池汽车上的应用。Based on the application requirements for new energy vehicles, the cycle efficiency and speed of hydrogen dehydrogenation of hydrogen storage devices greatly limit the application of organic hydrogen storage liquids in hydrogen fuel cell vehicles.
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancing the understanding of the general background of the present invention and should not be taken as an acknowledgment or any form of suggestion that the information constitutes the prior art that is already known to those skilled in the art.
发明内容Contents of the invention
本发明的目的在于提供一种铂/钼脱氢催化材料、制备方法及其应用，通过对活性成型进行优化组合，有效改善了脱氢效能，极大地提升了对液体储氢材料的催化脱氢能力。The purpose of the present invention is to provide a platinum/molybdenum dehydrogenation catalytic material, a preparation method and its application. By optimizing the combination of active molding, the dehydrogenation efficiency is effectively improved, and the catalytic dehydrogenation of liquid hydrogen storage materials is greatly improved. ability.
为实现上述目的，本发明的实施例提供了铂/钼脱氢催化材料，包括载体以及形成于载体上的催化组合物，所述催化组合物占催化材料总质量的0.75-1.5％，所述催化组合物包括铂元素和钼元素。In order to achieve the above object, embodiments of the present invention provide a platinum/molybdenum dehydrogenation catalytic material, including a carrier and a catalytic composition formed on the carrier, the catalytic composition accounts for 0.75-1.5% of the total mass of the catalytic material, and the The catalytic composition includes platinum and molybdenum.
在本发明的一个或多个实施方式中，催化组合物中铂元素与钼元素的质量比为1：(0.5-2)。In one or more embodiments of the present invention, the mass ratio of platinum element to molybdenum element in the catalytic composition is 1:(0.5-2).
在本发明的一个或多个实施方式中，铂元素至少源自如下任一：Pt(NO 3) 4、H 2PtCl 6。 In one or more embodiments of the present invention, the platinum element is at least derived from any one of the following: Pt(NO 3 ) 4 , H 2 PtCl 6 .
在本发明的一个或多个实施方式中，钼元素至少源自如下任一：钼酸、钼酸盐。In one or more embodiments of the present invention, the molybdenum element is at least derived from any of the following: molybdic acid and molybdate.
在本发明的一个或多个实施方式中，载体选自如下任一：氧化铝、TiO 2、Cr 2O 3、MnO 2、Fe 2O 3、CoO、NiO、CuO及ZrO 2。 In one or more embodiments of the present invention, the carrier is selected from any one of the following: alumina, TiO 2 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , CoO, NiO, CuO and ZrO 2 .
在本发明的一个或多个实施方式中，铂/钼脱氢催化材料的制备方法，其特征在于，包括如下步骤：配制含有铂源和钼源的混合溶液；将载体混合浸润到所述混合溶液，充分浸润后烘干，再在贫氧条件下烧结即可。In one or more embodiments of the present invention, the preparation method of platinum/molybdenum dehydrogenation catalytic material is characterized in that it includes the following steps: preparing a mixed solution containing platinum source and molybdenum source; Solution, fully soaked and dried, and then sintered under oxygen-poor conditions.
在本发明的一个或多个实施方式中，烘干为在80-100度烘干2-4小时。In one or more embodiments of the present invention, the drying is at 80-100 degrees for 2-4 hours.
在本发明的一个或多个实施方式中，贫氧条件为氢气条件。In one or more embodiments of the invention, the oxygen-depleted conditions are hydrogen conditions.
在本发明的一个或多个实施方式中，烧结为在贫氧条件下，升温至250-350度下，保持2-6小时。In one or more embodiments of the present invention, the sintering is carried out under oxygen-poor conditions, and the temperature is raised to 250-350 degrees, and kept for 2-6 hours.
在本发明的一个或多个实施方式中，如前述的铂/钼脱氢催化材料在液体储氢技术中的应用。In one or more embodiments of the present invention, the aforementioned platinum/molybdenum dehydrogenation catalytic material is used in liquid hydrogen storage technology.
与现有技术相比，根据本发明实施方式的铂/钼脱氢催化材料，其制备简单，组成稳 定，基体以及活性成分组成简单，同时具有较高的活性和抗毒性，能够有效地改善催化脱氢的效能。Compared with the prior art, the platinum/molybdenum dehydrogenation catalytic material according to the embodiment of the present invention has simple preparation, stable composition, simple composition of matrix and active components, high activity and anti-toxicity, and can effectively improve catalytic performance. dehydrogenation efficiency.
附图说明Description of drawings
图1是根据本发明一实施方式的不同组成的催化材料脱氢效能对比图。Fig. 1 is a comparison chart of dehydrogenation performance of catalytic materials with different compositions according to an embodiment of the present invention.
图2是根据本发明一实施方式的不同载体的催化材料脱氢效能对比图。Fig. 2 is a comparison chart of dehydrogenation performance of catalytic materials with different supports according to an embodiment of the present invention.
具体实施方式Detailed ways
下面结合附图，对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。The specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.
除非另有其它明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分，而并未排除其它元件或其它组成部分。Unless expressly stated otherwise, throughout the specification and claims, the term "comprise" or variations thereof such as "includes" or "includes" and the like will be understood to include the stated elements or constituents, and not Other elements or other components are not excluded.
为了形成有效的对比，以下所列实施例中，载体物理性质都采用同一的形态：颗粒尺寸3mm球形多孔颗粒，比表面积5平方米/克。In order to form an effective comparison, in the following examples, the physical properties of the carrier are all in the same form: spherical porous particles with a particle size of 3 mm and a specific surface area of 5 square meters per gram.
实施例1Example 1
催化剂制备：Catalyst preparation:
1.依据下表配置一定浓度的硝酸铂/钼酸混合溶液，溶剂为水；得溶液A1. Configure a certain concentration of platinum nitrate/molybdic acid mixed solution according to the following table, and the solvent is water; get solution A
2.使用等体积浸润法，将溶液A浸润入氧化铝载体；得前驱体B2. Use the equal volume infiltration method to infiltrate the solution A into the alumina carrier; obtain the precursor B
3.将前驱体B，放入烘箱中100度烘干2小时；得前驱体C3. Put the precursor B in an oven and dry it at 100 degrees for 2 hours; get the precursor C
4.将前驱体C放入管式马弗炉中，通入氢气后，升温至300度下，保持2小时；得催化剂。4. Put the precursor C into a tubular muffle furnace, feed hydrogen, raise the temperature to 300 degrees, and keep it for 2 hours; the catalyst is obtained.
脱氢效果测试方法：Dehydrogenation effect test method:
1.称取40g18氢-二苄基甲苯，2g催化剂，加入高温反应釜中；1. Weigh 40g of 18H-dibenzyltoluene and 2g of catalyst into the high temperature reaction kettle;
2.使用氢气反复置换高温反应釜；保持常压；2. Use hydrogen to replace the high-temperature reactor repeatedly; maintain normal pressure;
3.开启搅拌(300～1500pm)，开启升温350度保持。3. Turn on the stirring (300~1500pm), turn on the temperature and keep it at 350 degrees.
Figure PCTCN2021132234-appb-000001
Figure PCTCN2021132234-appb-000001
Figure PCTCN2021132234-appb-000002
Figure PCTCN2021132234-appb-000002
其中，“-”表示该催化物的效能为无催化效果。Wherein, "-" indicates that the performance of the catalyst has no catalytic effect.
如图1所示的，根据本发明优选实施方式的铂/钼脱氢催化材料，针对现有技术中脱氢催化剂的生产工序复杂、能耗高、成本高，催化剂的活性成分以及载体都成分复杂、且需要用到大量的昂贵材料，极大地增加了催化材料的应用成本。As shown in Figure 1, according to the platinum/molybdenum dehydrogenation catalytic material of the preferred embodiment of the present invention, the production process of the dehydrogenation catalyst in the prior art is complicated, the energy consumption is high, the cost is high, and the active components of the catalyst and the carrier are all components It is complex and requires a large amount of expensive materials, which greatly increases the application cost of catalytic materials.
实施例2Example 2
催化剂制备：Catalyst preparation:
1.依据下表配置一定浓度的硝酸铂/钼酸混合溶液，溶剂为无水酒精；得溶液A1. Configure a certain concentration of platinum nitrate/molybdic acid mixed solution according to the table below, and the solvent is absolute alcohol; get solution A
2.使用等体积浸润法，将溶液A浸润入TiO 2载体；得前驱体B 2. Use the equal volume infiltration method to infiltrate the solution A into the TiO 2 carrier; obtain the precursor B
3.将前驱体B，放入烘箱中80度烘干4小时；得前驱体C3. Put the precursor B in an oven and dry it at 80 degrees for 4 hours; get the precursor C
4.将前驱体C放入管式马弗炉中，通入氢气后，升温至325度下，保持5小时；得催化剂。4. Put the precursor C into a tubular muffle furnace, feed hydrogen, raise the temperature to 325 degrees, and keep it for 5 hours; the catalyst is obtained.
脱氢效果测试方法：Dehydrogenation effect test method:
1.称取40g18氢-二苄基甲苯，2g催化剂，加入高温反应釜中；1. Weigh 40g of 18H-dibenzyltoluene and 2g of catalyst into the high temperature reaction kettle;
2.使用氢气反复置换高温反应釜；保持常压；2. Use hydrogen to replace the high-temperature reactor repeatedly; maintain normal pressure;
3.开启搅拌(300～1500pm)，开启升温350度保持。3. Turn on the stirring (300~1500pm), turn on the temperature and keep it at 350 degrees.
Figure PCTCN2021132234-appb-000003
Figure PCTCN2021132234-appb-000003
其中，“-”表示该催化物的效能为无催化效果。Wherein, "-" indicates that the performance of the catalyst has no catalytic effect.
实施例3Example 3
催化剂制备：Catalyst preparation:
1.依据下表配置一定浓度的硝酸铂/钼酸混合溶液，溶剂为水；得溶液A1. Configure a certain concentration of platinum nitrate/molybdic acid mixed solution according to the following table, and the solvent is water; get solution A
2.使用等体积浸润法，将溶液A浸润入Cr 2O 3载体；得前驱体B 2. Use the equal volume infiltration method to infiltrate the solution A into the Cr 2 O 3 carrier; obtain the precursor B
3.将前驱体B，放入烘箱中80度烘干3小时；得前驱体C3. Put the precursor B in an oven and dry it at 80 degrees for 3 hours; get the precursor C
4.将前驱体C放入管式马弗炉中，通入氢气后，升温至275度下，保持4小时；得催化剂。4. Put the precursor C into a tubular muffle furnace, feed hydrogen, raise the temperature to 275 degrees, and keep it for 4 hours; the catalyst is obtained.
脱氢效果测试方法：Dehydrogenation effect test method:
1.称取40g18氢-二苄基甲苯，2g催化剂，加入高温反应釜中；1. Weigh 40g of 18H-dibenzyltoluene and 2g of catalyst into the high temperature reaction kettle;
2.使用氢气反复置换高温反应釜；保持常压；2. Use hydrogen to replace the high-temperature reactor repeatedly; maintain normal pressure;
3.开启搅拌(300～1500pm)，开启升温350度保持。3. Turn on the stirring (300~1500pm), turn on the temperature and keep it at 350 degrees.
Figure PCTCN2021132234-appb-000004
Figure PCTCN2021132234-appb-000004
Figure PCTCN2021132234-appb-000005
Figure PCTCN2021132234-appb-000005
其中，“-”表示该催化物的效能为无催化效果。Wherein, "-" indicates that the performance of the catalyst has no catalytic effect.
实施例4Example 4
催化剂制备：Catalyst preparation:
1.依据下表配置一定浓度的硝酸铂/钼酸混合溶液，溶剂为水；得溶液A1. Configure a certain concentration of platinum nitrate/molybdic acid mixed solution according to the following table, and the solvent is water; get solution A
2.使用等体积浸润法，将溶液A浸润入Fe 2O 3载体；得前驱体B 2. Use the equal volume infiltration method to infiltrate the solution A into the Fe 2 O 3 carrier; obtain the precursor B
3.将前驱体B，放入烘箱中90度烘干3小时；得前驱体C3. Put the precursor B in an oven at 90 degrees to dry for 3 hours; get the precursor C
4.将前驱体C放入管式马弗炉中，通入氢气后，升温至250度下，保持2小时；得催化剂。4. Put the precursor C into a tubular muffle furnace, feed hydrogen, raise the temperature to 250 degrees, and keep it for 2 hours; the catalyst is obtained.
脱氢效果测试方法：Dehydrogenation effect test method:
1.称取40g十氢萘，2g催化剂，加入高温反应釜中；1. Weigh 40g of decahydronaphthalene and 2g of catalyst, and add them to the high-temperature reaction kettle;
2.使用氢气反复置换高温反应釜；保持常压；2. Use hydrogen to replace the high-temperature reactor repeatedly; maintain normal pressure;
3.开启搅拌(300～1500pm)，开启升温350度保持。3. Turn on the stirring (300~1500pm), turn on the temperature and keep it at 350 degrees.
Figure PCTCN2021132234-appb-000006
Figure PCTCN2021132234-appb-000006
Figure PCTCN2021132234-appb-000007
Figure PCTCN2021132234-appb-000007
其中，“-”表示该催化物的效能为无催化效果。Wherein, "-" indicates that the performance of the catalyst has no catalytic effect.
实施例5Example 5
催化剂制备：Catalyst preparation:
1.依据下表配置一定浓度的硝酸铂/钼酸混合溶液，溶剂为无水酒精；得溶液A1. Configure a certain concentration of platinum nitrate/molybdic acid mixed solution according to the table below, and the solvent is absolute alcohol; get solution A
2.使用等体积浸润法，将溶液A浸润入ZrO 2载体；得前驱体B 2. Use the equal volume infiltration method to infiltrate the solution A into the ZrO 2 carrier; obtain the precursor B
3.将前驱体B，放入烘箱中100度烘干4小时；得前驱体C3. Put the precursor B in an oven at 100 degrees to dry for 4 hours; get the precursor C
4.将前驱体C放入管式马弗炉中，通入氢气后，升温至350度下，保持6小时；得催化剂。4. Put the precursor C into a tubular muffle furnace, feed hydrogen, raise the temperature to 350 degrees, and keep it for 6 hours; the catalyst is obtained.
脱氢效果测试方法：Dehydrogenation effect test method:
1.称取40g全氢咔唑，2g催化剂，加入高温反应釜中；1. Weigh 40g of perhydrocarbazole and 2g of catalyst, and add them to the high-temperature reaction kettle;
2.使用氢气反复置换高温反应釜；保持常压；2. Use hydrogen to replace the high-temperature reactor repeatedly; maintain normal pressure;
3.开启搅拌(300～1500pm)，开启升温350度保持。3. Turn on the stirring (300~1500pm), turn on the temperature and keep it at 350 degrees.
Figure PCTCN2021132234-appb-000008
Figure PCTCN2021132234-appb-000008
Figure PCTCN2021132234-appb-000009
Figure PCTCN2021132234-appb-000009
其中，“-”表示该催化物的效能为无催化效果。Wherein, "-" indicates that the performance of the catalyst has no catalytic effect.
如图2所示的，根据本发明优选实施方式的铂/钼脱氢催化材料，对多种载体都一定的适应性，当然通过图示的，也体现了一定的性能选择性，这可能与金属元素原子序数有一定的关联。As shown in Figure 2, the platinum/molybdenum dehydrogenation catalytic material according to the preferred embodiment of the present invention has certain adaptability to various supports. Of course, as shown in the figure, it also reflects a certain performance selectivity, which may be related to The atomic number of metal elements has a certain correlation.
通过上述实施例的罗列与比较表明，本发明选择的催化材料的组合，组成简单，有较强的稳定性，对多种类型的载体都有较强的适应性。The enumeration and comparison of the above examples show that the combination of catalytic materials selected in the present invention has simple composition, strong stability, and strong adaptability to various types of carriers.
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及 其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. These descriptions are not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling others skilled in the art to make and use various exemplary embodiments of the invention, as well as various Choose and change. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

  1. 一种铂/钼脱氢催化材料，其特征在于，包括载体以及形成于载体上的催化组合物，所述催化组合物占催化材料总质量的0.75-1.5％，所述催化组合物包括铂元素和钼元素。A platinum/molybdenum dehydrogenation catalytic material is characterized in that it includes a carrier and a catalytic composition formed on the carrier, the catalytic composition accounts for 0.75-1.5% of the total mass of the catalytic material, and the catalytic composition includes platinum element and molybdenum.
  2. 如权利要求1所述的铂/钼脱氢催化材料，其特征在于，所述催化组合物中铂元素与钼元素的质量比为1：(0.5-2)。The platinum/molybdenum dehydrogenation catalytic material according to claim 1, characterized in that the mass ratio of platinum element to molybdenum element in the catalytic composition is 1:(0.5-2).
  3. 如权利要求2所述的铂/钼脱氢催化材料，其特征在于，所述铂元素至少源自如下任一：Pt(NO 3) 4、H 2PtCl 6。 The platinum/molybdenum dehydrogenation catalytic material according to claim 2, wherein the platinum element is at least derived from any of the following: Pt(NO 3 ) 4 , H 2 PtCl 6 .
  4. 如权利要求2所述的铂/钼脱氢催化材料，其特征在于，所述钼元素至少源自如下任一：钼酸、钼酸盐。The platinum/molybdenum dehydrogenation catalytic material according to claim 2, wherein the molybdenum element is at least derived from any of the following: molybdic acid and molybdate.
  5. 如权利要求1所述的铂/钼脱氢催化材料，其特征在于，所述载体选自如下任一：氧化铝、TiO 2、Cr 2O 3、MnO 2、Fe 2O 3、CoO、NiO、CuO及ZrO 2。 The platinum/molybdenum dehydrogenation catalytic material according to claim 1, wherein the carrier is selected from any of the following: alumina, TiO 2 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , CoO, NiO , CuO and ZrO 2 .
  6. 铂/钼脱氢催化材料的制备方法，其特征在于，包括如下步骤：The preparation method of platinum/molybdenum dehydrogenation catalytic material is characterized in that, comprises the steps:
    配制含有铂源和钼源的混合溶液；Prepare a mixed solution containing platinum source and molybdenum source;
    将载体混合浸润到所述混合溶液，充分浸润后烘干，再在贫氧条件下烧结即可。The carrier is mixed and soaked into the mixed solution, fully soaked, dried, and then sintered under oxygen-poor conditions.
  7. 如权利要求6所述的铂/钼脱氢催化材料的制备方法，其特征在于，所述烘干为在80-100度烘干2-4小时。The preparation method of platinum/molybdenum dehydrogenation catalytic material according to claim 6, characterized in that the drying is at 80-100 degrees for 2-4 hours.
  8. 如权利要求6所述的铂/钼脱氢催化材料的制备方法，其特征在于，所述贫氧条件为氢气条件。The preparation method of platinum/molybdenum dehydrogenation catalytic material as claimed in claim 6, characterized in that the oxygen-poor condition is hydrogen condition.
  9. 如权利要求6所述的铂/钼脱氢催化材料的制备方法，其特征在于，所述烧结为在贫氧条件下，升温至250-350度下，保持2-6小时。The preparation method of platinum/molybdenum dehydrogenation catalytic material according to claim 6, characterized in that the sintering is carried out under oxygen-deficient conditions, and the temperature is raised to 250-350 degrees and kept for 2-6 hours.
  10. 铂/钼脱氢催化材料在液体储氢技术中的应用。Application of platinum/molybdenum dehydrogenation catalytic materials in liquid hydrogen storage technology.
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