An organic liquid hydrogen storage catalyst and method of preparation

Abstract

This invention discloses an organic liquid hydrogen storage catalyst and its preparation method, which mainly consists of a support, mixed metal salt, binder, water, and sponge. The preparation method utilizes the property that the sol-carrier coagulates into a gel after adding salt, and uses the sponge as a medium to manufacture an organic liquid hydrogenation and dehydrogenation catalyst product that resembles a sieve. This can effectively increase the contact area between the catalyst and the gas or liquid, ensure the uniform flow rate of the gas or liquid flowing through the catalyst cross section, and guarantee the stability of production and the efficiency of catalyst use.

Description

Technical Field

[0001] This invention belongs to the field of new energy, specifically to the field of hydrogen storage and transportation technology, and specifically relates to catalysts and preparation methods for hydrogenation and dehydrogenation of organic liquid hydrogen storage. Background Technology

[0002] With the development of society and economy, traditional fossil energy is being consumed in large quantities, resulting in massive carbon emissions and the greenhouse effect. Hydrogen energy is an important clean energy source to meet the needs of sustainable development and environmental friendliness. Hydrogen storage technology has always been a bottleneck in the development of hydrogen energy applications. At present, the main commercially available hydrogen storage methods are high-pressure gaseous hydrogen storage and cryogenic liquefaction hydrogen storage. Organic liquid hydrogen storage technology has been proposed as a new type of hydrogen storage technology. It achieves hydrogen storage by using an organic liquid hydrogen storage carrier containing unsaturated bonds and a reversible addition and dehydrogenation reaction with hydrogen. It can utilize the existing infrastructure for the transportation and use of fossil fuels, making storage convenient, safe to use, and with low supply chain construction costs. It is a beneficial supplement to existing hydrogen storage technologies.

[0003] Most existing hydrogenation and dehydrogenation catalysts suffer from poor thermal stability, rapid activity decline over long periods of operation, and susceptibility to poisoning by byproducts. Therefore, we propose an organic liquid hydrogen storage catalyst and its preparation method by focusing on the homogenization of active metals and increasing the contact area between the catalyst and the organic liquid hydrogen storage support. This method utilizes the gelation properties of silica sol with metal salt ions and combines them with the pore-forming properties of porous sponges, and can significantly improve the stability of organic liquid hydrogenation and dehydrogenation.

[0004] CN 111392691 A, A method for low-temperature dehydrogenation of fully hydrogenated organic liquid hydrogen storage materials catalyzed by palladium-based catalysts; CN 114733530 A, A hydrogenation catalyst for organic liquid hydrogen storage supports, its preparation method and application; CN114700074 A, A preparation method for a multi-element alloy catalyst, the multi-element alloy catalyst and its application; CN 115254141 A, A catalyst with micro-precious metal loading, its preparation method and its application; CN 118479417 A, A method for hydrogenation and dehydrogenation of heterocyclic organic liquid hydrogen storage supports; The catalysts obtained by the above methods have the following disadvantages: 1. The contact area between the organic liquid and the catalyst is small; 2. Organic liquids do not easily enter the interior of the pyrolysis agent block and flow effectively; 3. The catalyst is inefficient or unstable. Summary of the Invention

[0005] This invention provides an organic liquid hydrogen storage catalyst and its preparation method to overcome the shortcomings of existing technologies. The specific solution is as follows: An organic liquid hydrogen storage catalyst and its preparation method are characterized by comprising a support, a mixed metal salt, a binder, water, and a sponge, and the preparation method is as follows: Step 1. Weigh a certain mass of carrier, the mass of which is calculated on a dry basis; Step 2. Add the mixed metal salt and binder to the water and stir until homogeneous. If necessary, disperse by ball milling to obtain liquid A. Step 3. Add liquid A to the carrier and stir until homogeneous to obtain liquid B; Step 4. Use a sponge to absorb liquid B. After liquid B becomes a gel, put it into a drying kiln and dry it at 100-120 degrees Celsius to form a sponge cake. Step 5. Calcine the dried sponge cake from Step 4 at 250-1200 degrees Celsius. After the sponge burns off, a porous and highly permeable organic liquid hydrogen storage catalyst is obtained.

[0006] An organic liquid hydrogen storage catalyst and its preparation method are characterized by comprising a support, a mixed metal salt, a binder, and deionized water, and the preparation method is as follows: Step 1. Weigh a certain mass of carrier, the mass of which is calculated on a dry basis; Step 2. Add the mixed metal salt and binder to deionized water and stir until homogeneous. If necessary, disperse by ball milling to obtain liquid A. Step 3. Add liquid A to the carrier and stir until homogeneous to obtain liquid B; Step 4. Pour liquid B into a container of the desired shape. After liquid B becomes gel-like, send it into a drying kiln and dry it at 100-120 degrees Celsius to obtain the catalyst precursor. Step 5. Calcine the catalyst precursor at 250-1200 degrees Celsius to obtain a highly permeable organic liquid hydrogen storage catalyst.

[0007] The organic liquid hydrogen storage catalyst and its preparation method as described above are characterized in that the support is silica sol.

[0008] The adhesive is at least one of sodium carboxymethyl cellulose, polyvinyl acetate emulsion, styrene-acrylic emulsion, silicone-acrylic emulsion, acrylic emulsion, polyester emulsion, and epoxy emulsion.

[0009] The sponge is a common porous material with water absorption properties.

[0010] The mixed metal salt includes at least two of the following: nitrates, hydrochlorides, and carbonates of Pd, Pt, Ru, Rh, Co, Ni, Cu, Fe, Mo, Mn, Sn, Zn, Ir, La, Al, Na, K, and Ce.

[0011] The mixed metal salts include acetylacetone salts of Pd, Pt, Ru, Rh, Co, Ni, Cu, Fe, Mo, Mn, Sn, Zn, Ir, La, and Al, and at least two of NaCl and KCl.

[0012] The total mass fraction of metal elements contained in the organic liquid hydrogen storage catalyst is 3-20 wt%.

[0013] The organic liquid hydrogen storage catalyst produced by the above technology is used in the hydrogenation and dehydrogenation reactions of nitrogen heterocyclic organic liquid hydrogen storage carriers.

[0014] Compared with the prior art, the present invention can achieve the following technical effects: 1. This invention can effectively increase the specific surface area of ​​the catalyst; 2. The catalyst prepared by the method of the present invention has a porous structure with good air permeability, which allows the catalytic active components to fully contact and react with the gas or liquid, effectively improving the catalytic efficiency; 3. The organic liquid hydrogen storage catalyst and preparation method provided by the present invention can be manufactured according to the shape requirements of the equipment, fully meeting the process requirements and improving the stability of the catalytic reaction process.

[0015] Attached image description: Figure 1 This is a diagram showing the appearance of the organic liquid hydrogen storage catalyst of the present invention. Detailed Implementation

[0016] The embodiments of the present invention will be described in detail below with reference to the examples. The following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.

[0017] Example 1: 286 g of 35% silica sol, 60 g of nickel nitrate, 10 g of molybdenum nitrate, and 50 g of polyvinyl acetate emulsion; Its preparation method is as follows: Step 1. Weigh 286 grams of 35% silica sol. The dry weight of the carrier is approximately 100 grams. Step 2. Add nickel nitrate, molybdenum nitrate, and polyvinyl acetate emulsion to 240g of water in sequence and stir until homogeneous to obtain liquid A; Step 3. Add liquid A to the silica sol carrier and stir until homogeneous to obtain liquid B; Step 4. Pour liquid B into a container of the desired shape. After liquid B becomes gel-like, send it into a drying kiln and dry it at 100-120 degrees Celsius to obtain the catalyst precursor. Step 5. Calcine the catalyst precursor at 250-1200 degrees Celsius to obtain a highly permeable organic liquid hydrogenation catalyst.

[0018] Example 2: 286 g of 35% silica sol, 60 g of nickel nitrate, 10 g of molybdenum nitrate, and 50 g of polyvinyl acetate emulsion; Its preparation method is as follows: Step 1. Weigh 286 grams of 35% silica sol. The dry weight of the carrier is approximately 100 grams. Step 2. Add nickel nitrate, molybdenum nitrate, and polyvinyl acetate emulsion to 200g of water in sequence and stir until homogeneous to obtain liquid A; Step 3. Add liquid A to the silica sol carrier and stir until homogeneous to obtain liquid B; Step 4. Use a sponge to absorb liquid B. Once liquid B becomes a gel, put it into a drying kiln and dry it at 100-120 degrees Celsius to form a sponge cake. Step 5. Calcine the dried sponge cake from Step 4 at 250-1200 degrees Celsius. After the sponge burns off, a porous and highly permeable organic liquid hydrogenation catalyst is obtained.

[0019] Example 3: 286 g of 35% silica sol, 12 g of palladium nitrate, 10 g of ruthenium nitrate, and 50 g of polyvinyl acetate emulsion; Its preparation method is as follows: Step 1. Weigh 286 grams of 35% silica sol. The dry weight of the carrier is approximately 100 grams. Step 2. Add palladium nitrate, ruthenium nitrate, and polyvinyl acetate emulsion to 150g of water in sequence and stir until homogeneous to obtain liquid A; Step 3. Add liquid A to the silica sol carrier and stir until homogeneous to obtain liquid B; Step 4. Pour liquid B into a container of the desired shape. After liquid B becomes gel-like, send it into a drying kiln and dry it at 100-120 degrees Celsius to obtain the catalyst precursor. Step 5. Calcine the catalyst precursor at 250-1200 degrees Celsius to obtain a highly permeable organic liquid dehydrogenation catalyst.

[0020] Example 4: 286 g of 35% silica sol, 12 g of palladium nitrate, 10 g of ruthenium nitrate, and 50 g of polyvinyl acetate emulsion; Its preparation method is as follows: Step 1. Weigh 286 grams of 35% silica sol. The dry weight of the carrier is approximately 100 grams. Step 2. Add palladium nitrate, ruthenium nitrate, and polyvinyl acetate emulsion to 150g of water in sequence and stir until homogeneous to obtain liquid A; Step 3. Add liquid A to the silica sol carrier and stir until homogeneous to obtain liquid B; Step 4. Use a sponge to absorb liquid B. Once liquid B becomes a gel, put it into a drying kiln and dry it at 100-120 degrees Celsius to form a sponge cake. Step 5. Calcine the dried sponge cake from Step 4 at 250-1200 degrees Celsius. After the sponge burns off, a porous and highly permeable organic liquid dehydrogenation catalyst is obtained.

Claims

1. An organic liquid hydrogen storage catalyst and its preparation method, characterized in that... The components include a carrier, mixed metal salts, a binder, water, and a sponge. The preparation method is as follows: Step 1. Weigh a certain mass of carrier, the mass of which is calculated on a dry basis; Step 2. Add the mixed metal salt and binder to the water and stir until homogeneous. If necessary, disperse by ball milling to obtain liquid A. Step 3. Add liquid A to the carrier and stir until homogeneous to obtain liquid B; Step 4. Use a sponge to absorb liquid B. After liquid B becomes a gel, put it into a drying kiln and dry it at 100-120 degrees Celsius to form a sponge cake. Step 5. Calcine the dried sponge cake from Step 4 at 250-1200 degrees Celsius. After the sponge burns off, a porous and highly permeable organic liquid hydrogen storage catalyst is obtained.

2. An organic liquid hydrogen storage catalyst and its preparation method, characterized in that... The preparation method includes a carrier, mixed metal salts, a binder, and water, and is as follows: Step 1. Weigh a certain mass of carrier, the mass of which is calculated on a dry basis; Step 2. Add the mixed metal salt and binder to the water and stir until homogeneous. If necessary, disperse by ball milling to obtain liquid A. Step 3. Add liquid A to the carrier and stir until homogeneous to obtain liquid B; Step 4. Pour liquid B into a container of the desired shape. After liquid B becomes gel-like, send it into a drying kiln and dry it at 100-120 degrees Celsius to obtain the catalyst precursor. Step 5. Calcine the catalyst precursor at 250-1200 degrees Celsius to obtain a highly permeable organic liquid hydrogen storage catalyst.

3. The organic liquid hydrogen storage catalyst and its preparation method according to claims 1 and 2, characterized in that... The carrier is silica sol.

4. The organic liquid hydrogen storage catalyst and its preparation method according to claims 1 and 2, characterized in that, The adhesive is one of sodium carboxymethyl cellulose, polyvinyl acetate emulsion, styrene-acrylic emulsion, silicone-acrylic emulsion, acrylic emulsion, polyester emulsion, and epoxy emulsion.

5. The organic liquid hydrogen storage catalyst and its preparation method according to claims 1 and 2, characterized in that, The sponge is a common porous material with water absorption properties.

6. The organic liquid hydrogen storage catalyst and its preparation method according to claims 1 and 2, characterized in that, The mixed metal salt includes at least two of the following: nitrates, hydrochlorides, and carbonates of Pd, Pt, Ru, Rh, Co, Ni, Cu, Fe, Mo, Mn, Sn, Zn, Ir, La, Al, Na, K, and Ce.

7. The organic liquid hydrogen storage catalyst and its preparation method according to claims 1 and 2, characterized in that, The mixed metal salt includes at least two of the following: acetylacetone salts of Pd, Pt, Ru, Rh, Co, Ni, Cu, Fe, Mo, Mn, Sn, Zn, Ir, La, Al, NaCl, and KCl.

8. An organic liquid hydrogen storage catalyst and its preparation method, characterized in that, The organic liquid hydrogen storage catalyst is obtained by the preparation method of the organic liquid hydrogen storage catalyst according to any one of claims 1 and 7, wherein the total mass fraction of the metal elements contained in the organic liquid hydrogen storage catalyst is 3-20 wt%.

9. An organic liquid hydrogen storage catalyst and its preparation method, characterized in that, The organic liquid hydrogen storage catalyst of claim 8 is used in the hydrogenation and dehydrogenation reaction process of nitrogen heterocyclic organic liquid hydrogen storage carrier.

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