WO2023103822A1 - Hydrogen-carrying catalyst for liquid hydrogen storage, preparation method, and application - Google Patents
Hydrogen-carrying catalyst for liquid hydrogen storage, preparation method, and application Download PDFInfo
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- WO2023103822A1 WO2023103822A1 PCT/CN2022/134730 CN2022134730W WO2023103822A1 WO 2023103822 A1 WO2023103822 A1 WO 2023103822A1 CN 2022134730 W CN2022134730 W CN 2022134730W WO 2023103822 A1 WO2023103822 A1 WO 2023103822A1
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- 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
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
Definitions
- the invention relates to new energy liquid hydrogen storage and dehydrogenation technology, in particular to a hydrogen-carrying catalyst for liquid hydrogen storage, a preparation method and application.
- the object of the present invention is to provide a hydrogen-carrying catalyst for liquid hydrogen storage, preparation method and application, improve the carrier and processing technology, effectively improve the stability of the active component ruthenium on the surface distribution, and effectively reduce the chlorine
- the distribution state of the elements on the surface of the carrier enables the adjustment of catalyst performance and cost.
- embodiments of the present invention provide a hydrogen-carrying catalyst for liquid hydrogen storage, including a porous carrier, the carrier is pretreated with a water-soluble carbonate solution; the ruthenium element loaded on the surface of the carrier .
- the pretreatment of the carrier is obtained by fully soaking the carrier in the carbonate solution and then drying it.
- the carbonate solution is sodium carbonate solution or sodium bicarbonate solution or potassium carbonate solution or potassium bicarbonate solution or a mixed solution of at least the two.
- the total molar concentration of carbonate or bicarbonate in the carbonate solution is 0.01 ⁇ 0.1 mol/L.
- drying is drying at 80-120 degrees for 3-6 hours.
- drying further includes drying in the shade for 24-48 hours before drying.
- the preparation method of a hydrogen-carrying catalyst for liquid hydrogen storage includes the following steps: after fully infiltrating a porous carrier with a carbonate solution, and then drying to obtain a pretreated carrier A;
- the treated carrier A is fully infiltrated with the ruthenium source solution (soaking time 8-16h).
- the carrier after the infiltrated ruthenium source solution can be dried to obtain better sintering quality (the drying condition is 100-160 drying at 2-6 h), to obtain the carrier B loaded with ruthenium element; in the H 2 /H 2 O mixed gas environment, sintering and reducing the carrier B, to obtain a hydrogen-carrying catalyst for liquid hydrogen storage with ruthenium element loaded on the surface.
- condition of sintering reduction is sintering at 500-900 degrees for 2-6 hours.
- the H2O content in the H 2 /H 2 O mixed gas environment is 0.5-2wt.%.
- the aforementioned hydrogen-carrying catalyst for liquid hydrogen storage is used in liquid catalytic hydrogenation.
- the highly active Ru/Al 2 O is prepared by using the lower-priced ruthenium trichloride as the raw material through the optimized scheme 3 Catalyst, improve the support and processing technology, effectively improve the stability of the distribution of active ingredient ruthenium on the surface, and effectively reduce the distribution of chlorine on the surface of the support, thus realizing the improvement of catalyst performance and cost. Adjustment.
- Fig. 1 is the hydrogenation efficiency according to one embodiment of the present invention.
- curves 1-8 correspond to 11-18 of the present embodiment respectively, and each curve shows the reaction curve under different adjustments, and can see the impact and reduction of the carbonate treatment carrier on the catalytic performance in the figure The effect of water vapor in the atmosphere.
- the carrier was soaked in RuCl solution for 8 hours, separated and dried at 100 degrees for 3 hours;
- the present invention solves chloride ion from two aspects:
- Catalyst support treatment use 0.01-0.1mol/L carbonate solution to fully infiltrate the catalyst support, which can effectively limit the loaded RuCl 3 on the surface of the support, thereby preventing chloride ions from entering the interior of the support, so as to fully detach chlorine atoms.
- Ru can also be fixed on the surface of the carrier to improve the utilization rate of precious metals.
Abstract
Disclosed are a hydrogen-carrying catalyst for liquid hydrogen storage, a preparation method, and an application. The hydrogen-carrying catalyst for liquid hydrogen storage comprises: a porous carrier, the carrier being pretreated by a water-soluble carbonate solution; and ruthenium loaded on the surface of the carrier. According to the present invention, the stability of distribution of ruthenium, serving as an active component, on a surface is effectively improved, and meanwhile, the distribution state of chlorine on the surface of the carrier is effectively reduced, thereby achieving the adjustment of catalyst efficiency, costs and the like.
Description
本发明要求2021年12月06日向中国专利局提交的、申请号为2021114790000、发明名称为“液体储氢用载氢催化剂、制备方法及应用”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 2021114790000 and the title of the invention "Hydrogen-carrying catalyst for liquid hydrogen storage, preparation method and application" submitted to the China Patent Office on December 06, 2021, and the entire content of the application Incorporated herein by reference.
本发明关于新能源液体储氢脱氢技术，特别是关于一种液体储氢用载氢催化剂、制备方法及应用。The invention relates to new energy liquid hydrogen storage and dehydrogenation technology, in particular to a hydrogen-carrying catalyst for liquid hydrogen storage, a preparation method and application.
在液相有机储氢的催化剂技术中，发现同一贵金属的不同原料制备的催化剂催化效果差异很大，分别以三氯化钌和亚硝酰基硝酸合钌制备的Ru-0.5％/Al
2O
3催化剂为例，亚硝酰基硝酸合钌制备的催化剂催化效果是三氯化钌制备的5倍以上。经过分析，发现两种催化剂中氯离子含量的显著差异导致了催化剂效果的差别。综上在改善催化剂的元素分布，尤其是利用三氯化钌制备催化剂过程中如何有效的去除氯离子则成为重中之重。
In the liquid-phase organic hydrogen storage catalyst technology, it was found that the catalytic effect of the catalyst prepared by different raw materials of the same noble metal was very different. Ru-0.5%/Al 2 O 3 Taking the catalyst as an example, the catalytic effect of the catalyst prepared by ruthenium nitrosyl nitrate is more than 5 times that of ruthenium trichloride. After analysis, it was found that the significant difference in the content of chloride ions in the two catalysts resulted in the difference in catalyst effect. In summary, improving the element distribution of the catalyst, especially how to effectively remove chloride ions in the process of using ruthenium trichloride to prepare the catalyst has become a top priority.
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 intended to increase 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 of ordinary skill in the art.
发明内容Contents of the invention
本发明的目的在于提供一种液体储氢用载氢催化剂、制备方法及应用，提高针对载体和加工工艺进行改进，有效地提高了活性成分钌在表面分布的稳定性，同时有效地降低了氯元素在载体表面的分布状态，从而实现了对催化剂效能和成本等方面调整。The object of the present invention is to provide a hydrogen-carrying catalyst for liquid hydrogen storage, preparation method and application, improve the carrier and processing technology, effectively improve the stability of the active component ruthenium on the surface distribution, and effectively reduce the chlorine The distribution state of the elements on the surface of the carrier enables the adjustment of catalyst performance and cost.
为实现上述目的，本发明的实施例提供了液体储氢用载氢催化剂，包括，具有多 孔的载体，所述载体为经过水溶性的碳酸盐溶液预处理的；负载于载体表面的钌元素。In order to achieve the above object, embodiments of the present invention provide a hydrogen-carrying catalyst for liquid hydrogen storage, including a porous carrier, the carrier is pretreated with a water-soluble carbonate solution; the ruthenium element loaded on the surface of the carrier .
在本发明的一个或多个实施方式中，载体的预处理为将所述载体在所述碳酸盐溶液中充分浸润后干燥得到。In one or more embodiments of the present invention, the pretreatment of the carrier is obtained by fully soaking the carrier in the carbonate solution and then drying it.
在本发明的一个或多个实施方式中，碳酸盐溶液为碳酸钠溶液或碳酸氢钠溶液或碳酸钾溶液或碳酸氢钾溶液或者至少两者的混合溶液。In one or more embodiments of the present invention, the carbonate solution is sodium carbonate solution or sodium bicarbonate solution or potassium carbonate solution or potassium bicarbonate solution or a mixed solution of at least the two.
在本发明的一个或多个实施方式中，碳酸盐溶液中碳酸根或者碳酸氢根总摩尔浓度为0.01～0.1mol/L。In one or more embodiments of the present invention, the total molar concentration of carbonate or bicarbonate in the carbonate solution is 0.01˜0.1 mol/L.
在本发明的一个或多个实施方式中，干燥为在80-120度下烘干3-6h。In one or more embodiments of the present invention, drying is drying at 80-120 degrees for 3-6 hours.
在本发明的一个或多个实施方式中，干燥还包括在烘干前阴干24-48h。In one or more embodiments of the present invention, drying further includes drying in the shade for 24-48 hours before drying.
在本发明的一个或多个实施方式中，液体储氢用载氢催化剂的制备方法，包括如下步骤：以碳酸盐溶液充分浸润多孔的载体后，然后干燥得到预处理后的载体A；预处理后的载体A，以钌源溶液充分浸润(浸润时间8-16h)，这里可以对浸润后钌源溶液后的载体进行烘干，以获得较好的烧结质量(烘干条件为100-160度下烘干2-6h)，获得加载钌元素后的载体B；在H
2/H
2O混合气环境下，烧结还原载体B，获得表面负载钌元素的液体储氢用载氢催化剂。
In one or more embodiments of the present invention, the preparation method of a hydrogen-carrying catalyst for liquid hydrogen storage includes the following steps: after fully infiltrating a porous carrier with a carbonate solution, and then drying to obtain a pretreated carrier A; The treated carrier A is fully infiltrated with the ruthenium source solution (soaking time 8-16h). Here, the carrier after the infiltrated ruthenium source solution can be dried to obtain better sintering quality (the drying condition is 100-160 drying at 2-6 h), to obtain the carrier B loaded with ruthenium element; in the H 2 /H 2 O mixed gas environment, sintering and reducing the carrier B, to obtain a hydrogen-carrying catalyst for liquid hydrogen storage with ruthenium element loaded on the surface.
在本发明的一个或多个实施方式中，烧结还原的条件为500～900度烧结2-6h。In one or more embodiments of the present invention, the condition of sintering reduction is sintering at 500-900 degrees for 2-6 hours.
在本发明的一个或多个实施方式中，H
2/H
2O混合气环境中H2O含量为0.5-2wt.％。
In one or more embodiments of the present invention, the H2O content in the H 2 /H 2 O mixed gas environment is 0.5-2wt.%.
在本发明的一个或多个实施方式中，如前述的液体储氢用载氢催化剂在液体催化加氢中的应用。In one or more embodiments of the present invention, the aforementioned hydrogen-carrying catalyst for liquid hydrogen storage is used in liquid catalytic hydrogenation.
与现有技术相比，根据本发明实施方式的液体储氢用载氢催化剂、制备方法及应用，通过优化方案使用价格较低的三氯化钌为原料制备出高活性的Ru/Al
2O
3催化剂，提高针对载体和加工工艺进行改进，有效地提高了活性成分钌在表面分布的稳定性，同时有效地降低了氯元素在载体表面的分布状态，从而实现了对催化剂效能和成本等方面调整。
Compared with the prior art, according to the hydrogen-carrying catalyst for liquid hydrogen storage, the preparation method and the application according to the embodiment of the present invention, the highly active Ru/Al 2 O is prepared by using the lower-priced ruthenium trichloride as the raw material through the optimized scheme 3 Catalyst, improve the support and processing technology, effectively improve the stability of the distribution of active ingredient ruthenium on the surface, and effectively reduce the distribution of chlorine on the surface of the support, thus realizing the improvement of catalyst performance and cost. Adjustment.
图1是根据本发明一实施方式的加氢效率。Fig. 1 is the hydrogenation efficiency according to one embodiment of the present invention.
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.
实施例组1 Example group 1
催化剂制备方法：Catalyst preparation method:
使用如下表所示浓度Na
2CO
3溶液充分浸润催化剂载体8h，分离后在100度下烘干3h，即得到处理后的载体(下同)；
Use the Na 2 CO 3 solution with the concentration shown in the table below to fully infiltrate the catalyst carrier for 8 hours, and dry it at 100 degrees for 3 hours after separation to obtain the treated carrier (the same below);
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将处理后的催化剂载体加入RuCl
3溶液中浸润8h，分离后在100度下烘干3h；
Add the treated catalyst carrier into the RuCl3 solution for soaking for 8 hours, and dry it at 100 degrees for 3 hours after separation;
使用H
2/H
2O混合气，还原浸润RuCl
3的催化剂载体2h，降温后得到催化剂；
Use H 2 /H 2 O mixed gas to reduce the catalyst carrier soaked in RuCl 3 for 2 hours, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
如图1所示的，其中曲线1-8分别对应本实施例的11-18，各曲线展示了不同调节下的反应曲线，图中可以看到碳酸盐处理载体对催化效能的影响和还原性气氛中水蒸气的影响。As shown in Figure 1, wherein curves 1-8 correspond to 11-18 of the present embodiment respectively, and each curve shows the reaction curve under different adjustments, and can see the impact and reduction of the carbonate treatment carrier on the catalytic performance in the figure The effect of water vapor in the atmosphere.
实施例组2 Example group 2
催化剂制备方法：Catalyst preparation method:
使用如下表所示浓度K
2CO
3溶液充分浸润催化剂载体8h，分离后在80度下烘干4h；
Use the K 2 CO 3 solution with the concentration shown in the table below to fully infiltrate the catalyst carrier for 8 hours, and dry it at 80 degrees for 4 hours after separation;
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将处理后的催化剂载体加入RuCl
3溶液中浸润10h，分离后在110度下烘干2h；
Add the treated catalyst carrier into the RuCl3 solution for soaking for 10 hours, and dry it at 110 degrees for 2 hours after separation;
使用H
2/H
2O混合气，还原浸润RuCl
3的催化剂载体2h，降温后得到催化剂；
Use H 2 /H 2 O mixed gas to reduce the catalyst carrier soaked in RuCl 3 for 2 hours, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
实施例组3 Example group 3
催化剂制备方法：Catalyst preparation method:
使用如下表所示浓度KHCO
3溶液充分浸润催化剂载体8h，分离后在120度下烘干6h；
Use the KHCO 3 solution with the concentration shown in the table below to fully infiltrate the catalyst carrier for 8 hours, and dry it at 120 degrees for 6 hours after separation;
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将处理后的催化剂载体加入RuCl
3溶液中浸润12h，分离后在140度下烘干4h；
Add the treated catalyst carrier into the RuCl3 solution for soaking for 12 hours, and dry it at 140 degrees for 4 hours after separation;
使用H
2/H
2O混合气，还原浸润RuCl
3的催化剂载体4h，降温后得到催化剂；
Use H 2 /H 2 O mixed gas to reduce the catalyst carrier soaked in RuCl 3 for 4 hours, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
实施例组4Example group 4
催化剂制备方法：Catalyst preparation method:
使用如下表所示浓度NaHCO
3溶液充分浸润催化剂载体8h，分离后在90度下烘干5h；
Use the NaHCO 3 solution with the concentration shown in the table below to fully infiltrate the catalyst carrier for 8 hours, and dry it at 90 degrees for 5 hours after separation;
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将处理后的催化剂载体加入RuCl
3溶液中浸润14h，分离后阴干48h，再在150度下烘干5h；
Add the treated catalyst carrier into the RuCl3 solution for soaking for 14 hours, dry it in the shade for 48 hours after separation, and then dry it at 150 degrees for 5 hours;
使用H
2/H
2O混合气，还原浸润RuCl
3的催化剂载体6h，降温后得到催化剂；
Use H 2 /H 2 O mixed gas to reduce the catalyst carrier soaked in RuCl 3 for 6 hours, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
对比例组1 Comparative example group 1
催化剂制备方法：Catalyst preparation method:
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将载体加入RuCl
3溶液中浸润8h，分离后在100度下烘干3h；
The carrier was soaked in RuCl solution for 8 hours, separated and dried at 100 degrees for 3 hours;
使用H
2/H
2O混合气，还原浸润RuCl
3的催化剂载体2h，降温后得到催化剂；
Use H 2 /H 2 O mixed gas to reduce the catalyst carrier soaked in RuCl 3 for 2 hours, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
对比例组2 Comparative example group 2
催化剂制备方法：Catalyst preparation method:
使用0.01mol/LNa
2CO
3溶液充分浸润催化剂载体8h，分离后在100度下烘干3h，即得到处理后的载体(下同)；
Use 0.01mol/L Na 2 CO 3 solution to fully infiltrate the catalyst carrier for 8 hours, and dry it at 100 degrees for 3 hours after separation to obtain the treated carrier (the same below);
如下表配置合适浓度的RuCl
3水溶液；
Configure the appropriate concentration of RuCl 3 aqueous solution as shown in the table below;
将处理后的催化剂载体加入RuCl
3溶液中浸润8h，分离后在100度下烘干3h；
Add the treated catalyst carrier into the RuCl3 solution for soaking for 8 hours, and dry it at 100 degrees for 3 hours after separation;
使用H
2还原浸润RuCl
3的催化剂载体2h，降温后得到催化剂；
Use H2 to reduce the catalyst carrier soaked in RuCl3 for 2h, and obtain the catalyst after cooling down;
催化剂效果测试方法Catalyst effect test method
1.称取40g苄基甲苯，2g催化剂，加入高温高压反应釜中；1. Weigh 40g of benzyltoluene and 2g of catalyst, and put them into a high temperature and high pressure reactor;
2.使用氢气反复置换高温高压反应釜；2. Use hydrogen to replace the high-temperature and high-pressure reactor repeatedly;
3.开启搅拌(300～1500pm)，开启升温(180～250度)；3. Turn on the stirring (300~1500pm), turn on the heating (180~250 degrees);
4.温度达到200度后，通入氢气，保持氢气压力(范围5～9MPa)4. After the temperature reaches 200 degrees, feed hydrogen to maintain the hydrogen pressure (range 5 ~ 9MPa)
本发明，从两方面解决氯离子：The present invention solves chloride ion from two aspects:
催化剂载体处理，使用0.01～0.1mol/L碳酸盐溶液充分浸润催化剂载体，可以有效的将负载的RuCl
3限制在载体表面，从而防止氯离子进入载体内部，从而实现将氯原子充分脱离。同样可以将Ru固定在载体表面，提高贵金属利用率。
Catalyst support treatment, use 0.01-0.1mol/L carbonate solution to fully infiltrate the catalyst support, which can effectively limit the loaded RuCl 3 on the surface of the support, thereby preventing chloride ions from entering the interior of the support, so as to fully detach chlorine atoms. Ru can also be fixed on the surface of the carrier to improve the utilization rate of precious metals.
在催化剂还原过程中，在还原气H
2中加入水蒸气，有效的将氯离子从催化剂中带出。
During the catalyst reduction process, water vapor is added to the reducing gas H2 to effectively take chloride ions out of the catalyst.
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)
- 一种液体储氢用载氢催化剂，其特征在于，包括，A hydrogen-carrying catalyst for liquid hydrogen storage, characterized in that it comprises,具有多孔的载体，所述载体为经过水溶性的碳酸盐溶液预处理的；Having a porous carrier pretreated with a water-soluble carbonate solution;负载于载体表面的钌元素。Ruthenium element loaded on the surface of the carrier.
- 如权利要求1所述的液体储氢用载氢催化剂，其特征在于，所述载体的预处理为将所述载体在所述碳酸盐溶液中充分浸润后干燥得到。The hydrogen-carrying catalyst for liquid hydrogen storage according to claim 1, characterized in that the pretreatment of the carrier is obtained by fully soaking the carrier in the carbonate solution and then drying.
- 如权利要求1或2所述的液体储氢用载氢催化剂，其特征在于，所述碳酸盐溶液为碳酸钠溶液或碳酸氢钠溶液或碳酸钾溶液或碳酸氢钾溶液或者至少两者的混合溶液。The hydrogen-carrying catalyst for liquid hydrogen storage as claimed in claim 1 or 2, wherein the carbonate solution is sodium carbonate solution or sodium bicarbonate solution or potassium carbonate solution or potassium bicarbonate solution or at least both mixture.
- 如权利要求3所述的液体储氢用载氢催化剂，其特征在于，所述碳酸盐溶液中碳酸根或者碳酸氢根总摩尔浓度为0.01～0.1mol/L。The hydrogen-carrying catalyst for liquid hydrogen storage according to claim 3, characterized in that the total molar concentration of carbonate or bicarbonate in the carbonate solution is 0.01-0.1 mol/L.
- 如权利要求2所述的液体储氢用载氢催化剂，其特征在于，所述干燥为在80-120度下烘干3-6h。The hydrogen-carrying catalyst for liquid hydrogen storage according to claim 2, wherein said drying is drying at 80-120 degrees for 3-6 hours.
- 如权利要求5所述的液体储氢用载氢催化剂，其特征在于，所述干燥还包括在烘干前阴干24-48h。The hydrogen-carrying catalyst for liquid hydrogen storage according to claim 5, wherein said drying further comprises drying in the shade for 24-48 hours before drying.
- 如权利要求1-6任一所述的液体储氢用载氢催化剂的制备方法，其特征在于，所包括如下步骤：The method for preparing a hydrogen-carrying catalyst for liquid hydrogen storage according to any one of claims 1-6, characterized in that it comprises the following steps:以碳酸盐溶液充分浸润多孔的载体后，然后干燥得到预处理后的载体A；After fully infiltrating the porous carrier with a carbonate solution, and then drying to obtain the pretreated carrier A;预处理后的载体A，以钌源溶液充分浸润，获得加载钌元素后的载体B；The pretreated carrier A is fully infiltrated with the ruthenium source solution to obtain the carrier B loaded with ruthenium;在H 2/H 2O混合气环境下，烧结还原载体B，获得表面负载钌元素的液体储氢用载氢催化剂。 In the environment of H 2 /H 2 O mixed gas, the carrier B is sintered and reduced to obtain a hydrogen-carrying catalyst for liquid hydrogen storage with ruthenium element supported on the surface.
- 如权利要求7所述的液体储氢用载氢催化剂的制备方法，其特征在于，所述烧结还原的条件为500～900度烧结2-6h。The preparation method of the hydrogen-carrying catalyst for liquid hydrogen storage according to claim 7, characterized in that the condition of the sintering reduction is sintering at 500-900 degrees for 2-6 hours.
- 如权利要求7所述的液体储氢用载氢催化剂的制备方法，其特征在于，所述H 2/H 2O混合气环境中含量为0.5-2wt.％。 The preparation method of the hydrogen-carrying catalyst for liquid hydrogen storage according to claim 7, characterized in that the content of the H 2 /H 2 O mixed gas environment is 0.5-2wt.%.
- 如权利要求1-6任一所述的液体储氢用载氢催化剂在液体催化加氢中的应用。The application of the hydrogen-carrying catalyst for liquid hydrogen storage as described in any one of claims 1-6 in liquid catalytic hydrogenation.
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| CN114160128A (en) * | 2021-12-06 | 2022-03-11 | 苏州金宏气体股份有限公司 | Hydrogen-carrying catalyst for liquid hydrogen storage, preparation method and application |
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- 2021-12-06 CN CN202111479000.0A patent/CN114160128A/en active Pending
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| US4407733A (en) * | 1978-11-11 | 1983-10-04 | Bayer Aktiengesellschaft | Supported catalysts and process for their preparation |
| JPH11226401A (en) * | 1998-02-17 | 1999-08-24 | Mitsubishi Chemical Corp | Production of hydrogenation catalyst |
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