阅读说明：本技术 水制氢催化剂、其制备方法及水制氢方法 (Catalyst for water hydrogen production, preparation method thereof and water hydrogen production method ) 是由 白艳芳 于 2019-09-30 设计创作，主要内容包括：本发明提供了一种水制氢催化剂、其制备方法及水制氢方法。该水制氢催化剂包括催化活性组分和粘结剂,该催化活性组分包括单质铝、单质铁、氧化锌、二硫化钼、二氧化锰和金属氯化物。本申请采用上述催化活性组分对水进行催化,在催化剂相对于水过量的情况下,其中产物气体中只有氢气不存在氧气,因此,一般不需要进行氧气分离防爆处理,从而也降低了水制氢后提纯成本；而且上述各组分即可起到高效的催化作用,不需要使用铂等贵金属组分,因此催化剂成本较低；同时,采用本申请的上述水制氢催化剂,在相对温和的条件下1kg催化剂与足量水反应,可产生至少30kg的氢气,综合制氢成本约为10元/kg,实现了低成本移动环保制氢。(The invention provides a catalyst for hydrogen production from water, a preparation method thereof and a method for hydrogen production from water. The catalyst for hydrogen production from water comprises a catalytic active component and a binder, wherein the catalytic active component comprises elemental aluminum, elemental iron, zinc oxide, molybdenum disulfide, manganese dioxide and metal chloride. The catalytic active components are adopted to catalyze water, and under the condition that the catalyst is excessive relative to water, only hydrogen in product gas does not contain oxygen, so that oxygen separation and explosion-proof treatment is not required generally, and the purification cost of the water after hydrogen production is reduced; moreover, the components can play a role in high-efficiency catalysis, and precious metal components such as platinum and the like are not needed, so that the catalyst is low in cost; meanwhile, 1kg of catalyst reacts with enough water under relatively mild conditions to generate at least 30kg of hydrogen, the comprehensive hydrogen production cost is about 10 yuan/kg, and low-cost mobile environment-friendly hydrogen production is realized.)

1. The catalyst for hydrogen production from water comprises a catalytic active component and a binder, and is characterized in that the catalytic active component comprises elemental aluminum, elemental iron, zinc oxide, molybdenum disulfide, manganese dioxide and metal chloride.

2. The catalyst for hydrogen production from water according to claim 1, wherein the catalytically active components comprise, in parts by weight: 13-40 parts of the simple substance aluminum, 4-20 parts of the simple substance iron, 10-25 parts of the zinc oxide, 4-9 parts of the molybdenum disulfide, 4-9 parts of manganese dioxide and 8-25 parts of the metal chloride.

3. The catalyst for hydrogen production from water as claimed in claim 2, wherein the catalytic active component comprises 13 to 40 parts by weight of the simple substance aluminum, 4 to 20 parts by weight of the simple substance iron, 10 to 25 parts by weight of the zinc oxide, 4 to 9 parts by weight of the molybdenum disulfide, 4 to 9 parts by weight of manganese dioxide and 8 to 25 parts by weight of the metal chloride.

4. Catalyst for the production of hydrogen from water according to claim 1, characterized in that the metal chloride is an alkali metal chloride, preferably sodium chloride.

5. The catalyst for hydrogen production from water according to claim 1, wherein the elemental aluminum, the elemental iron, the zinc oxide, the molybdenum disulfide and the manganese dioxide are all powders, and preferably, the elemental aluminum, the elemental iron, the zinc oxide, the molybdenum disulfide and the manganese dioxide are each a powder having a particle size of 200-500 meshes.

6. The catalyst for hydrogen production from water according to claim 4, wherein the catalytic active component is composed of 14 parts by weight of the elemental aluminum, 4 parts by weight of the elemental iron, 25 parts by weight of the zinc oxide, 9 parts by weight of the molybdenum disulfide, 9 parts by weight of manganese dioxide, and 8 parts by weight of the sodium chloride.

7. The catalyst for hydrogen production from water according to claim 1, wherein the binder is one or a combination of water glass and paste, and the amount of the binder is preferably 20-30% relative to the amount of the catalytically active component.

8. A method for preparing the catalyst for hydrogen production from water according to any one of claims 1 to 7, wherein the method for preparing comprises:

mixing a catalytically active component and a binder to form a slurry mixture;

and (3) sequentially carrying out pressurization standing treatment, heating treatment and cooling on the muddy mixture to obtain the water hydrogen production catalyst.

9. The method according to claim 8, wherein the pressure of the pressure-maintaining treatment is 0.4 to 0.6MPa for 1 to 3 hours, and preferably the temperature of the heat treatment is 200 to 300 ℃ for 2 to 6 hours.

10. A method for producing hydrogen from water, which is characterized by comprising the following steps: in a closed container, catalyzing water by using a catalyst at 90-200 ℃ to obtain hydrogen, wherein the mass ratio of the catalyst to the water is higher than 1: 270 which catalyst is a water-producing hydrogen catalyst as claimed in any one of claims 1 to 7.

Technical Field

The invention relates to the field of hydrogen production from water, in particular to a catalyst for hydrogen production from water, a preparation method thereof and a method for hydrogen production from water.

Background

Hydrogen is an ideal secondary energy, but at present, the preparation of hydrogen mainly adopts the mode of fossil fuel and chemical raw materials, the problem of high carbon emission is faced in the production process, the electric power required by the hydrogen production by water electrolysis is very expensive, and even if renewable energy sources such as abandoned wind and abandoned light are considered to be used for generating electricity and then producing hydrogen, the problem of hydrogen storage and transportation is also faced, because the location of the abandoned wind and abandoned light is often an underdeveloped area of industry, and the demand of hydrogen is very low. In hydrogen storage and transportation, the problems of high hydrogen storage and transportation cost still exist in the conventional modes of high-pressure gas tanks, liquid hydrogen storage, solid hydrogen storage and the like.

Disclosure of Invention

The invention mainly aims to provide a catalyst for hydrogen production from water, a preparation method thereof and a method for hydrogen production from water, so as to solve the problem of high hydrogen production cost in the prior art.

In order to achieve the above object, according to one aspect of the present invention, there is provided a catalyst for hydrogen production from water, comprising a catalytically active component and a binder, the catalytically active component comprising elemental aluminum, elemental iron, zinc oxide, molybdenum disulfide, manganese dioxide and a metal chloride.

Further, the catalytic active components comprise the following components in parts by weight: 13-40 parts of simple substance aluminum, 4-20 parts of simple substance iron, 10-25 parts of zinc oxide, 4-9 parts of molybdenum disulfide, 4-9 parts of manganese dioxide and 8-25 parts of metal chloride.

Furthermore, the catalytic active component comprises, by weight, 13-40 parts of simple substance aluminum, 4-20 parts of simple substance iron, 10-25 parts of zinc oxide, 4-9 parts of molybdenum disulfide, 4-9 parts of manganese dioxide and 8-25 parts of metal chloride.

Further, the metal chloride is an alkali metal chloride, preferably sodium chloride.

Further, the simple substance aluminum, the simple substance iron, the zinc oxide, the molybdenum disulfide and the manganese dioxide are all powder, and preferably, the simple substance aluminum, the simple substance iron, the zinc oxide, the molybdenum disulfide and the manganese dioxide are powder with the particle size of 200-500 meshes.

Further, the above-mentioned catalytically active component is composed of 14 parts by weight of elemental aluminum, 4 parts by weight of elemental iron, 25 parts by weight of zinc oxide, 9 parts by weight of molybdenum disulfide, 9 parts by weight of manganese dioxide and 8 parts by weight of sodium chloride.

The binder is one or a combination of water glass and paste, and the amount of the binder relative to the catalytic active component is preferably 20-30%.

According to another aspect of the present invention, there is provided a method for preparing a catalyst for hydrogen production from water according to any one of the above, the method comprising: mixing a catalytically active component and a binder to form a slurry mixture; and (3) sequentially carrying out pressurization standing treatment, heating treatment and cooling on the muddy mixture to obtain the hydrolysis hydrogen production catalyst.

Further, the pressure of the pressure standing treatment is 0.4 to 0.6MPa, the time is 1 to 3 hours, the temperature of the heating treatment is preferably 200 to 300 ℃, and the time is preferably 2 to 6 hours.

According to another aspect of the present invention, there is provided a method for producing hydrogen from water, comprising: in a closed container, a catalyst is adopted to catalyze water at 90-200 ℃ to obtain hydrogen, and the catalyst is any one of the above catalysts for producing hydrogen from water.

By applying the technical scheme of the invention, the water is catalyzed by the catalytic active component, wherein only hydrogen in product gas does not contain oxygen, so that oxygen separation explosion-proof treatment is not needed, and the treatment cost after hydrogen production from water is reduced; moreover, the components can play a role in high-efficiency catalysis, and precious metal components such as platinum and the like are not needed, so that the catalyst is low in cost; meanwhile, by adopting the catalyst for hydrogen production from water, at least 30kg of hydrogen can be produced by adjusting the process conditions and reacting 1kg of catalyst with sufficient water under relatively mild conditions, the cost for hydrogen production is calculated to be about 10 yuan/kg by comprehensively considering the depreciation of fixed assets, the cost for heating the catalyst raw materials, water and the like, the cost is reduced to have economic application value, and the low-cost mobile environment-friendly hydrogen production is realized.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As mentioned above, the catalyst for hydrogen production from water in the prior art has a high cost, or the cost is not high but the carbon emission is high, which results in a high cost for hydrogen production, or the external cost for hydrogen production is high.

In an exemplary embodiment of the present application, a catalyst for hydrogen production from water is provided, which includes a catalytically active component and a binder, wherein the catalytically active component includes elemental aluminum, elemental iron, zinc oxide, molybdenum disulfide, manganese dioxide and a metal chloride.

The catalyst for hydrogen production by using water can solve the storage and transportation problem of dehydrogenation, and realize mobile hydrogen production and hydrogen production at any time and any place; secondly, the environment-friendly hydrogen production can be realized, the catalysts are all common simple substances or compounds in nature, the energy consumption required in the preparation process is extremely low, and the method is a thorough clean hydrogen production mode; thirdly, from the economic point of view, the hydrogen production cost has a great popularization effect and economic feasibility.

The catalytic active components are adopted to catalyze water, and under the condition that the catalyst is excessive relative to water, only hydrogen in product gas does not contain oxygen, so that oxygen separation explosion-proof treatment is not needed, and the post-treatment cost of hydrogen production from water is reduced; moreover, the components can play a role in high-efficiency catalysis, and precious metal components such as platinum and the like are not needed, so that the catalyst is low in cost; meanwhile, by adopting the catalyst for hydrogen production from water, at least 30kg of hydrogen can be produced by adjusting the process conditions and reacting 1kg of catalyst with sufficient water under relatively mild conditions, the cost for hydrogen production is calculated to be about 10 yuan/kg by comprehensively considering the depreciation of fixed assets and the heating cost of catalyst raw materials, water and water, the cost is reduced to have economic application value, and the low-cost mobile environment-friendly hydrogen production is realized.

1kg of catalyst is reacted with a sufficient amount of water, calculated as at least 30kg of hydrogen produced (at least 270kg of water is required since the hydrogen is entirely derived from water, the molecular weight ratio of hydrogen to water being 1: 9), the excess of said catalyst with respect to water being: "catalyst: water "in a mass ratio higher than 1: 270.

in order to further improve the catalytic efficiency, the catalytic active component preferably comprises the following components in parts by weight: 13-40 parts of simple substance aluminum, 4-20 parts of simple substance iron, 10-25 parts of zinc oxide, 4-9 parts of molybdenum disulfide, 4-9 parts of manganese dioxide and 8-25 parts of metal chloride. On the basis of ensuring the catalytic efficiency, in order to further control the cost, the catalytic active component preferably comprises 13-40 parts by weight of simple substance aluminum, 4-20 parts by weight of simple substance iron, 10-25 parts by weight of zinc oxide, 4-9 parts by weight of molybdenum disulfide, 4-9 parts by weight of manganese dioxide and 8-25 parts by weight of metal chloride.

The metal chloride used in the present application may be an alkali metal chloride, preferably sodium chloride for further cost control.

In one embodiment of the present application, in order to enhance the exertion of the effects of each component of the catalytic active component, the simple substance aluminum, the simple substance iron, the zinc oxide, the molybdenum disulfide, and the manganese dioxide are preferably powders, and further preferably, the simple substance aluminum, the simple substance iron, the zinc oxide, the molybdenum disulfide, and the manganese dioxide are each powders having a particle size of 200 to 500 meshes.

In a preferred embodiment, the catalytically active component consists of 14 parts by weight of elemental aluminium, 4 parts by weight of elemental iron, 25 parts by weight of zinc oxide, 9 parts by weight of molybdenum disulphide, 9 parts by weight of manganese dioxide and 8 parts by weight of sodium chloride. The catalytic effect of the catalytic active component with the composition is more prominent.

The binder is mainly used for forming the catalytic active component, the binder can be selected from the binder types commonly used in the prior art, preferably the binder is one or a combination of water glass and paste, and on the basis of forming the catalytic active component, the use amount of the binder relative to the catalytic active component is preferably 20-30% in order to increase the content of the catalytic active component as much as possible. The finished product of the catalyst for hydrogen production from water is ensured to have the porosity not less than 2% and the aperture between 0.2 mm and 1mm by utilizing the binder, thereby increasing the reaction area and ensuring the continuous and durable hydrogen production in unit time.

In another exemplary embodiment of the present application, there is provided a method of preparing a catalyst for hydrogen production from water according to any one of the above, the method comprising: mixing a catalytically active component and a binder to form a slurry mixture; and (3) sequentially carrying out pressurization standing treatment, heating treatment and cooling on the muddy mixture to obtain the water hydrogen production catalyst. The preparation method has simple flow and does not need special equipment, so that the preparation cost of the catalyst for hydrogen production from water is lower.

To improve the uniformity of dispersion of the ingredients of the catalytically active component, the ingredients may be mixed, for example, in a powder mixer to form a premix, which is then mixed with the binder to form a paste-like mixture.

The pressurizing is mainly used for increasing the compactness of the hydrolysis hydrogen production catalyst and improving the convenience of the hydrolysis hydrogen production catalyst during application, the dispersibility of elements in the standing process is further improved, and the pressurizing can be carried out by adopting formers in different shapes so as to obtain the hydrolysis hydrogen production catalysts in different shapes. The heat treatment is to volatilize the moisture in the binder to form a porous structure to facilitate the contact of water with the catalytically active component. Tests prove that the pressure of the pressurizing and standing treatment is preferably 0.4-0.6 MPa, the time is preferably 1-3 hours, the temperature of the heating treatment is preferably 200-300 ℃, and the time is preferably 2-6 hours, so that the obtained hydrolysis hydrogen production catalyst has high catalytic efficiency and long service life. Within the above range, the higher the temperature and pressure, the better.

In another exemplary embodiment of the present application, there is provided a method for producing hydrogen from water, including: in a closed container, catalyzing water by using a catalyst at 90-200 ℃ to obtain hydrogen, wherein the mass ratio of the catalyst to the water is higher than 1: 270, the catalyst is any one of the above catalysts for producing hydrogen from water.

The catalytic conditions of the catalyst for hydrogen production by hydrolysis are relatively mild, and the catalytic efficiency is increased along with the temperature rise, so that a person skilled in the art can select a proper catalytic temperature according to an application scene, for example, a relatively high temperature can be adopted in a fixed scene, and if the catalyst is used for a hydrogen-burning automobile, the temperature can be below 120 ℃.

The advantageous effects of the present application will be further described below with reference to examples and comparative examples.

Example 1

The composition of the catalytic active component is as follows: 1.3 kg of simple substance aluminum, 0.9 kg of simple substance iron, 2 kg of zinc oxide, 0.6 kg of molybdenum disulfide, 0.7 kg of manganese dioxide and 2.5 kg of sodium chloride. The simple substance aluminum, the simple substance iron, the zinc oxide, the molybdenum disulfide and the manganese dioxide are all powder bodies, and the particle size is 200-500 meshes.

Placing the materials in a powder mixer for fully mixing for 20 minutes to form mixed powder, uniformly mixing the mixed powder and 2.5 kg of water glass in a fixed container to form a mud-shaped mixture, placing the mud-shaped mixture in a square forming container, adding 4-6 atmospheres, standing for 2 hours for forming, taking out the formed mud-shaped mixture from the forming container, and baking for 4 hours at 250 ℃; after baking, the catalyst for hydrogen production by water in the example 1 is obtained by placing in the air and radiating to room temperature, and then the catalyst is packaged and sealed by a sealed shading waterproof bag.

Example 2

The difference from example 1 is that the composition of the catalytically active component is: 2.3 kg of simple substance aluminum, 1.2 kg of simple substance iron, 1.5 kg of zinc oxide, 0.5 kg of molybdenum disulfide, 0.5 kg of manganese dioxide and 1.5 kg of sodium chloride.

Example 3

The difference from example 1 is that the composition of the catalytically active component is: 1.4 kg of simple substance aluminum, 0.4 kg of simple substance iron, 2.5 kg of zinc oxide, 0.9 kg of molybdenum disulfide, 0.9 kg of manganese dioxide and 0.8 kg of sodium chloride.

Example 4

The difference from example 1 is that the composition of the catalytically active component is: 3 kg of simple substance aluminum, 2 kg of simple substance iron, 1kg of zinc oxide, 0.4 kg of molybdenum disulfide, 0.4 kg of manganese dioxide and 1.8 kg of sodium chloride.

Example 5

The difference from example 1 is that the composition of the catalytically active component is: 2 kg of simple substance aluminum, 1kg of simple substance iron, 1.7 kg of zinc oxide, 0.7 kg of molybdenum disulfide, 0.6 kg of manganese dioxide and 2 kg of sodium chloride.

Example 6

The difference from example 1 is that the binder is a paste, and the baking temperature is 200 ℃ and the baking time is 2 hours.

Example 7

The difference from example 1 is that the baking temperature was 300 ℃ and the baking time was 6 hours.

Example 8

The difference from the embodiment 1 is that the particle size of zinc oxide is 400 to 700 mesh.

Example 9

The difference from example 1 is that the sodium chloride is replaced by potassium chloride of the same mass.

Comparative example 1

The difference from example 3 is that the catalyst is free of molybdenum disulphide and zinc oxide.

The catalysts of each example and comparative example were used to catalyze water at 90 deg.C, 120 deg.C, 160 deg.C, and 200 deg.C in a stainless steel closed vessel to obtain hydrogen. The amount of catalyst used, the amount of water used and the mass of hydrogen obtained in 10, 12, 15 and 20 days are shown in Table 1.

It is worth noting that the water hydrogen production catalyst is not a simple metal hydrogen production principle, so the reaction is mild and lasts for a long time.

TABLE 1

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:

the catalyst for hydrogen production by using water can solve the storage and transportation problem of dehydrogenation, and realize mobile hydrogen production and hydrogen production at any time and any place; secondly, the environment-friendly hydrogen production can be realized, the catalysts are all common simple substances or chemical combination of nature, the energy consumption required by the preparation process is extremely low, and the method is a thorough clean hydrogen production mode; thirdly, from the economic point of view, the hydrogen production cost has a great popularization effect and economic feasibility.

The catalytic active components are adopted to catalyze water, and under the condition that the catalyst is excessive relative to water, only hydrogen in product gas does not contain oxygen, so that oxygen separation explosion-proof treatment is not needed, and the post-treatment cost of hydrogen production from water is reduced; moreover, the components can play a role in high-efficiency catalysis, and precious metal components such as platinum and the like are not needed, so that the catalyst is low in cost; meanwhile, by adopting the catalyst for hydrogen production from water, at least 30kg of hydrogen can be produced by adjusting the process conditions and reacting 1kg of catalyst with sufficient water under relatively mild conditions, the cost for hydrogen production is calculated to be about 10 yuan/kg by comprehensively considering the depreciation of fixed assets and the heating cost of catalyst raw materials, water and water, the cost is reduced to have economic application value, and the low-cost mobile environment-friendly hydrogen production is realized.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.