CN111620678B - Organic composite porous ceramic material and preparation method thereof - Google Patents
Organic composite porous ceramic material and preparation method thereof Download PDFInfo
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- CN111620678B CN111620678B CN202010458240.1A CN202010458240A CN111620678B CN 111620678 B CN111620678 B CN 111620678B CN 202010458240 A CN202010458240 A CN 202010458240A CN 111620678 B CN111620678 B CN 111620678B
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses an organic composite porous ceramic material and a preparation method thereof, and relates to the technical field of porous ceramic processing. The organic composite porous ceramic material disclosed by the invention is prepared by uniformly mixing and grinding components into mixed powder, then adding a water-soluble adhesive and water into the mixed powder, uniformly mixing, freeze-drying to prepare a porous ceramic precursor, and sintering the porous ceramic precursor at a high temperature. The organic composite porous ceramic material provided by the invention has high porosity and uniform pore distribution, and the size and the shape of pores can be controlled. The invention can be used for storing hydrogen, has the characteristics of high hydrogen storage capacity, simple hydrogen absorption and desorption operation, high temperature and high pressure resistance and the like, has good cycle stability, can be repeatedly used, and has high strength and difficult deformation of prepared products.
Description
Technical Field
The invention belongs to the technical field of porous ceramic processing, and particularly relates to an organic composite porous ceramic material and a preparation method thereof.
Background
The porous ceramic material is prepared by taking high-quality raw materials such as corundum, silicon carbide, cordierite and the like as main materials through molding and a special high-temperature sintering process. The porous ceramic material has the advantages of high temperature and high pressure resistance, acid, alkali and organic medium corrosion resistance, good biological inertia, controllable pore structure, high open porosity, long service life, good product regeneration performance and the like. The porous ceramic material is suitable for precise filtration and separation of various media, high-pressure gas exhaust silencing, gas distribution, electrolytic diaphragm and the like. The existing porous ceramic material is mainly burnt out or dissolved at high temperature by adding pore-forming agent, and a cavity is left, the size and the shape of the pore are easy to control, the process is simple, but the uniformity of reducing gas is poor, and the porosity is low.
Hydrogen is an ideal clean fuel and an important secondary energy source in the future. The existing hydrogen storage methods include liquefied hydrogen storage, compressed hydrogen storage and metal hydride hydrogen storage, and hydrogen storage materials are required in a high-pressure container and a liquid hydrogen storage tank. The hydrogen storage material is a material which can repeatedly and reversibly (usually over ten thousand times) absorb and release hydrogen under a normal mild condition, and is also called a hydrogen storage alloy or a hydrogen storage metal compound. The material can absorb hydrogen rapidly under a certain temperature and hydrogen pressure, and can release hydrogen when the temperature is properly increased or the hydrogen pressure is reduced. Existing hydrogen storage materials are essentially certain transition group metals, alloys or intermetallics that are susceptible to interaction with hydrogen. Since these metal materials have a specific crystal structure, hydrogen atoms easily enter into the interstices of their crystal lattices and form metal hydrides therewith. Hydrogen is weakly bonded to these metals and is released from the metals upon heating or changing the hydrogen pressure. This uptake and release of hydrogen into the metal depends on the phase equilibrium relationship of the metal and hydrogen and is limited by temperature, pressure and composition.
In practical application, a hydrogen storage material such as metal oxide, complex hydride or amide is generally put into a container with a valve to form a hydrogen storage device. However, because the hydrogen storage material in the container has good fluidity, the hydrogen storage material can flow and accumulate in the hydrogen storage device in the hydrogen absorption and desorption process, so that the container is deformed or damaged; the coordination hydride and the amino compound are easy to form the self-agglomeration phenomenon of powder in the hydrogen absorption and desorption process, so that the hydrogen absorption and desorption reaction speed is reduced; the hydrogen storage material powder has poor thermal conductivity, and is liable to cause slow or even stop of hydrogen absorption and desorption. In the prior art, a hydrogen storage tank is generally a metal tank, a hydrogen storage material is arranged in the metal tank, and in the process of absorbing and releasing hydrogen, if the operation is improper, the heat is improperly led out after the hydrogen storage tank is heated, so that the pressure of the hydrogen storage tank is easily overlarge, and the hydrogen storage tank explodes; and because the hydrogen storage tank inhales hydrogen in the heating process, the pressure in the hydrogen storage tank is large, and the hydrogen storage tank cannot collide in the transportation process, otherwise the hydrogen storage tank is easy to explode, and the life and property safety of people is harmed.
At present, the hydrogen storage alloy and the composite hydrogen storage material are widely applied, the heat transfer performance of the hydrogen storage alloy is good, the hydrogen storage alloy is not easy to absorb, expand and thin, but the hydrogen absorption and desorption operation is complex, namely the hydrogen absorption and desorption process needs heating and pressurizing, and the hydrogen storage capacity is reduced; the composite hydrogen storage material has high hydrogen storage capacity, but high hydrogen absorption and desorption temperature and poor circulation stability. The Chinese patent CN108746655A discloses a method for preparing a multi-element hydrogen storage composite material, the multi-element alloy hydrogen storage composite material prepared by the method has higher hydrogen storage density and low hydrogen absorption and desorption temperature, but has poorer cycle stability, and the hydrogen absorption and desorption process still needs heating. Further, a hydrogen storage alloy block produced by using a hydrogen storage alloy and a pore-forming agent is a porous hydrogen storage alloy, and has a simple production process, a low cost, and a simple operation of hydrogen absorption and desorption, but has a low hydrogen storage capacity, is not resistant to high pressure, and is easily deformed.
Disclosure of Invention
The invention provides an organic composite porous ceramic material, which mainly aims to improve the porosity of porous ceramic, ensure uniform pore distribution and control the size and the shape of pores. The invention can be used for storing hydrogen, has the characteristics of high hydrogen storage capacity, simple hydrogen absorption and desorption operation, high temperature and high pressure resistance and the like, has good cycle stability, can be repeatedly used, and has high strength and difficult deformation of prepared products.
In order to realize the purpose of the invention, the invention provides an organic composite porous ceramic material which is prepared from the following raw materials in parts by mass: 10-15 parts of silicon dioxide, 50-70 parts of diatomite, 5-10 parts of aluminum powder and 15-30 parts of modified cellulose, wherein the preparation method comprises the following steps:
(1) modified cellulose: adding a silane coupling agent into a solvent for dissolving, then adding a proper amount of acetic acid, adjusting the pH value to 4, soaking plant cellulose into the solution at the temperature of 60-80 ℃ for 9-12h, taking out, filtering, drying and ball-milling to obtain modified cellulose, wherein the mass ratio of the plant cellulose to the silane coupling agent is (5-6): 1;
(2) uniformly mixing silicon dioxide, aluminum powder, kieselguhr and modified cellulose, grinding into mixed powder, adding a water-soluble adhesive and water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain a porous ceramic precursor;
(3) loading the porous ceramic precursor into a hot-pressing mold, sintering at high temperature of 500 ℃ in the atmosphere of reducing gas and keeping the temperature for 1-2h to prepare a porous ceramic blank;
(4) and (3) roasting the porous ceramic blank at the high temperature of 1200 ℃ with nitrogen as protective gas, keeping the temperature for 3-6h, cooling to room temperature along with the furnace, and removing to obtain the composite porous ceramic material.
Further, the modified cellulose has an average particle diameter of 2 to 4 μm.
Furthermore, the average grain diameters of the silicon dioxide and the aluminum powder are both 5-8 μm,
further, the diatomite has an average particle size of 10 to 20 μm.
Further, the preparation method of the plant cellulose in the step (1) comprises the following steps: drying plant straw, pulverizing, hydrolyzing in 75% sulfuric acid solution for 10min, neutralizing with NaOH solution, washing with distilled water to neutrality, and drying.
Further, the mass ratio of the mixed powder, the water-soluble adhesive and the water in the step (2) is 1: (0.02-0.04): (1.2-1.4).
Further, the water-soluble adhesive is one or two of polyvinyl alcohol and carboxymethyl cellulose.
Further, the freeze-drying method in the step (2) is as follows: the freeze drying is divided into a freezing part and a drying part, the freezing temperature is-40 to-30 ℃, and the freezing time is 2 to 3 hours; the drying temperature is-20-10 ℃, the drying time is 18-24h, and the vacuum degree during the drying period is kept at 7-15 Pa.
The application of the organic composite porous ceramic material in hydrogen storage materials.
The invention achieves the following beneficial effects:
1. the silicon dioxide, the aluminum powder, the diatomite and the modified cellulose are mixed and then combined in the water-soluble binder, water is selected as a pore-forming agent, and a porous ceramic precursor is preliminarily formed through a freeze-drying process.
2. According to the invention, the modified cellulose can be subjected to cross-linking reaction with metal oxides in silicon dioxide and diatomite under the action of the water-soluble adhesive and water to prepare a network compound, and the network compound is sintered and carbonized at high temperature, so that the porosity of the porous ceramic is further improved, the pore size of the porous ceramic can be adjusted according to the particle size of the modified cellulose, and the porosity of the porous ceramic can be adjusted through the content of the modified cellulose.
3. The aluminum powder in the components reacts with water at high temperature to generate aluminum hydroxide, and then the aluminum hydroxide is sintered in a reducing gas atmosphere to generate aluminum oxide and release hydrogen. The alumina can improve the compactness of the porous ceramic, and improve the mechanical strength, temperature resistance and pressure resistance of the porous ceramic; the hydrogen gas generated at the same time can increase the porosity of the porous ceramic. The porosity of the porous ceramic can be adjusted by changing the content of the aluminum powder.
4. The diatomite has a natural porous structure and a large specific surface area, so that the diatomite has a good adsorption effect, and the porous ceramic prepared by the diatomite has high porosity as a matrix of an organic composite porous ceramic material, and can be used as an adsorption material due to excellent adsorption performance, so that the hydrogen storage capacity is large. The addition of silicon dioxide in the components further improves the adsorption capacity of the porous ceramic and further increases the hydrogen storage capacity.
5. When the organic composite porous ceramic material is used as a hydrogen storage material, hydrogen is absorbed under pressure, and in the hydrogen releasing process, only the hydrogen inlet and the hydrogen outlet are opened, and the hydrogen absorbing and releasing process does not need heating, so that the organic composite porous ceramic material is simple to operate and safe to use. The organic composite porous ceramic material has the characteristics of high temperature and high pressure resistance, and the deformation phenomenon of the tank body can not be generated in the hydrogen absorption process because the porous ceramic body bears most of the pressure of hydrogen; in the process of improper pressurization operation or transportation collision, explosion caused by overlarge pressure in the hydrogen storage tank can be avoided, and the life and property safety of people is protected.
6. The invention adopts diatomite as a matrix, and prepares the organic composite porous ceramic material with high porosity by a freeze drying process and sintering carbonization of a modified cellulose network compound, and the organic composite porous ceramic material has excellent mechanical properties and high temperature and high pressure resistance. The aluminum powder reacts to generate aluminum oxide and hydrogen in the sintering process, so that the compactness of the porous ceramic is improved, and the porosity of the porous ceramic is improved. The diatomite and the silicon dioxide have good adsorption performance, so that the porous ceramic hydrogen storage material has excellent hydrogen storage performance, namely, the hydrogen storage capacity is more than 10 times of the volume of the porous ceramic, and the phenomenon of swelling can not be generated in the hydrogen absorption process.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The organic composite porous ceramic material, the method for preparing the same, and the method for preparing the same according to the present invention will be described with reference to the following embodiments.
Example 1: organic composite porous ceramic material A1
The preparation method of the organic composite porous ceramic material A1 comprises the following steps:
(1) modified cellulose: adding silane coupling agent into solvent for dissolving, then adding proper amount of acetic acid, adjusting pH value to 4, soaking plant cellulose in the solution for 9-12h at 60-80 ℃, taking out, filtering, drying, and ball-milling to obtain modified cellulose with particle size of 2 μm. Wherein the mass ratio of the plant cellulose to the silane coupling agent is 5: 1.
(2) Uniformly mixing 10g of silicon dioxide, 5g of aluminum powder, 70g of diatomite and 15g of modified cellulose, grinding into mixed powder, adding 3g of hydroxymethyl cellulose and 120g of water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain the porous ceramic precursor. Wherein the average particle diameter of the silicon dioxide and the aluminum powder is 5-8 μm, and the average particle diameter of the diatomite is 10-20 μm.
(3) Loading the porous ceramic precursor into a hot-pressing mold, sintering at high temperature of 500 ℃ in the atmosphere of reducing gas and keeping the temperature for 1-2h to prepare a porous ceramic blank;
(4) and (3) roasting the porous ceramic blank at the temperature of 1200-1400 ℃ by taking nitrogen as protective gas, keeping the temperature for 3-6h, cooling to room temperature along with the furnace, and removing to obtain the organic composite porous ceramic material A1.
The preparation method of the plant cellulose in the step (1) comprises the following steps: drying plant straw, pulverizing, hydrolyzing in 75% sulfuric acid solution for 10min, neutralizing with NaOH solution, washing with distilled water to neutrality, and drying.
The freeze drying method in the step (2) comprises the following steps: the freeze drying is divided into a freezing part and a drying part, the freezing temperature is-40 to-30 ℃, and the freezing time is 2 to 3 hours; the drying temperature is-20-10 ℃, the drying time is 18-24h, and the vacuum degree during the drying period is kept at 7-15 Pa.
Example 2: organic composite porous ceramic material A2
The preparation method of the organic composite porous ceramic material A2 comprises the following steps:
(1) modified cellulose: adding silane coupling agent into solvent for dissolving, then adding proper amount of acetic acid, adjusting pH value to 4, soaking plant cellulose in the solution for 9-12h at 60-80 ℃, taking out, filtering, drying, and ball-milling to obtain modified cellulose with particle size of 3 μm. Wherein the mass ratio of the plant cellulose to the silane coupling agent is 6: 1.
(2) Uniformly mixing 15g of silicon dioxide, 10g of aluminum powder, 55g of diatomite and 20g of modified cellulose, grinding into mixed powder, adding 2g of polyvinyl alcohol and 130g of water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain the porous ceramic precursor. Wherein the average particle diameter of the silicon dioxide and the aluminum powder is 5-8 μm, and the average particle diameter of the diatomite is 10-20 μm.
(3) The specific procedure is as in example 1.
(4) Referring to example 1, an organic composite porous ceramic material a2 was prepared.
The method for producing plant cellulose in the step (1) and the method for freeze-drying in the step (2) are the same as those in example 1, and the specific steps are as in example 1.
Example 3: organic composite porous ceramic material A3
The preparation method of the organic composite porous ceramic material A3 comprises the following steps:
(1) modified cellulose: adding silane coupling agent into solvent for dissolving, then adding proper amount of acetic acid, adjusting pH value to 4, soaking plant cellulose in the solution for 9-12h at 60-80 ℃, taking out, filtering, drying, and ball-milling to obtain modified cellulose with particle size of 4 μm. Wherein the mass ratio of the plant cellulose to the silane coupling agent is 6: 1.
(2) Uniformly mixing 15g of silicon dioxide, 5g of aluminum powder, 50g of diatomite and 30g of modified cellulose, grinding into mixed powder, adding 4g of polyvinyl alcohol and 140g of water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain the porous ceramic precursor. Wherein the average particle diameter of the silicon dioxide and the aluminum powder is 5-8 μm, and the average particle diameter of the diatomite is 10-20 μm.
(3) The specific procedure is as in example 1.
(4) Referring to example 1, an organic composite porous ceramic material a3 was prepared.
The method for producing plant cellulose in the step (1) and the method for freeze-drying in the step (2) are the same as those in example 1, and the specific steps are as in example 1.
Example 4: organic composite porous ceramic material A4
The preparation method of the organic composite porous ceramic material A4 comprises the following steps:
(1) modified cellulose: adding silane coupling agent into solvent for dissolving, then adding proper amount of acetic acid, adjusting pH value to 4, soaking plant cellulose in the solution for 9-12h at 60-80 ℃, taking out, filtering, drying, and ball-milling to obtain modified cellulose with particle size of 3 μm. Wherein the mass ratio of the plant cellulose to the silane coupling agent is 5: 1.
(2) Uniformly mixing 12g of silicon dioxide, 8g of aluminum powder, 60g of diatomite and 20g of modified cellulose, grinding into mixed powder, adding 2g of polyvinyl alcohol, 2g of hydroxymethyl cellulose and 130g of water into the mixed powder, uniformly mixing, reacting for 4-6h at the temperature of 60-80 ℃, and freeze-drying to obtain the porous ceramic precursor. Wherein the average particle diameter of the silicon dioxide and the aluminum powder is 5-8 μm, and the average particle diameter of the diatomite is 10-20 μm.
(3) The specific procedure is as in example 1.
(4) Referring to example 1, an organic composite porous ceramic material a4 was prepared.
The method for producing plant cellulose in the step (1) and the method for freeze-drying in the step (2) are the same as those in example 1, and the specific steps are as in example 1.
Comparative example 1:
(1) uniformly mixing 20g of silicon dioxide, 10g of aluminum powder and 70g of diatomite, grinding into mixed powder, adding 4g of polyvinyl alcohol and 120g of water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain the porous ceramic precursor. Wherein the average particle diameter of the silicon dioxide and the aluminum powder is 5-8 μm, and the average particle diameter of the diatomite is 10-20 μm. The freeze-drying process was the same as in example 1.
(2) Loading the porous ceramic precursor into a hot-pressing mold, sintering at high temperature of 500 ℃ in the atmosphere of reducing gas and keeping the temperature for 1-2h to prepare a porous ceramic blank;
(3) and (3) roasting the porous ceramic blank at the temperature of 1200-1400 ℃ by taking nitrogen as protective gas, keeping the temperature for 3-6h, cooling to room temperature along with the furnace, and removing to obtain the composite porous ceramic material B1.
The organic composite porous ceramic materials A1, A2, A3 and A4 prepared in the above examples 1 to 4 and B1 prepared in comparative example 1 were tested for mechanical strength and porosity, and the results are shown in Table 1.
TABLE 1 TABLE of results of comparative tests on the properties of examples 1-4 and comparative example 1
| A1 | A2 | A3 | A4 | B1 | |
| Compressive strength/MPa | 18 | 17 | 15 | 20 | 22 |
| Pore size/μm | 5-20 | 10-30 | 5-35 | 20-30 | 5-100 |
| Porosity/% | 78 | 83 | 82 | 85 | 60 |
According to the results of the comparative tests of the above examples 1 to 4, it can be seen that the organic composite ceramic material of the present invention has good compressive strength and uniform pore size distribution; after the modified cellulose is added, the porosity of the porous ceramic is increased, so that the porosity can reach 85%.
Implementation 5: organic composite porous ceramic material A5
The preparation method of the organic composite porous ceramic material A5 of example 5 is the same as the preparation method of A4 in example 4, and the specific steps refer to example 4. Unlike example 4, the modified cellulose had a particle size of 2 μm.
Implementation 6: organic composite porous ceramic material A6
The preparation method of the organic composite porous ceramic material a6 of example 6 is the same as the preparation method of a4 in example 4, and the specific steps refer to example 4. Unlike example 4, the modified cellulose had a particle size of 4 μm.
Comparative example 2:
the preparation method of the organic composite porous ceramic material B2 of comparative example 2 is the same as the preparation method of A4 in example 4, and the specific steps refer to example 4. Unlike example 4, the modified cellulose had a particle size of 5 μm.
Comparative example 3:
the preparation method of the organic composite porous ceramic material B3 of comparative example 3 is the same as the preparation method of A4 in example 4, and the specific steps refer to example 4. Unlike example 4, the modified cellulose had a particle size of 1 μm.
Comparative example 4:
the preparation method of the organic composite porous ceramic material B4 of comparative example 4 is the same as the preparation method of A4 in example 4, and the specific steps refer to example 4. Different from example 4, there were 12g of silica, 8g of aluminum powder, 68g of diatomaceous earth and 12g of modified cellulose.
Comparative example 5:
the preparation method of the organic composite porous ceramic material B5 of comparative example 5 is the same as the preparation method of A4 in example 4, and the specific steps refer to example 4. Different from example 4, the paint comprises 10g of silica, 8g of aluminum powder, 50g of diatomite and 32g of modified cellulose.
The mechanical properties and porosities of A4, A5 and A6 obtained in examples 4 to 6 and B2, B3, B4 and B5 obtained in comparative examples 2 to 5 were measured, and the results are shown in Table 2.
TABLE 2 TABLE of results of comparative tests on the properties of examples 4-6 and comparative examples 2-5
From the results of the comparative tests of the above examples 4 to 6, it can be seen that too much or too little modified cellulose is added to the organic composite ceramic material of the present invention, which reduces the porosity thereof and affects the compressive strength of the porous ceramic; too large or too small particle size of the modified cellulose will increase the particle size distribution range of the porous ceramic and make the particle size distribution uneven.
The following specific examples will describe the use of the organic composite porous ceramic material of the present invention in a hydrogen storage material.
Example 7: preparation of hydrogen storage tank C1 by organic composite ceramic material
The method for preparing the hydrogen storage tank C1 by using the organic composite ceramic material comprises the following steps:
(1) loading the porous ceramic precursor prepared in the embodiment 1 into a hot-pressing mold, wherein the hot-pressing mold is determined according to the required shape of a hydrogen storage tank, and sintering at the high temperature of 300-500 ℃ in the atmosphere of reducing gas for 1-2h to prepare a porous ceramic blank;
(2) and (3) roasting the porous ceramic blank at the temperature of 1200-1400 ℃ by taking nitrogen as protective gas, keeping the temperature for 3-6h, cooling to room temperature along with the furnace, and removing to obtain the organic composite porous ceramic body.
(3) And (3) bonding a metal shell on the outer wall of the organic composite porous ceramic body, wherein the top end of the metal shell is provided with a hydrogen inlet and a hydrogen outlet, and the hydrogen inlet and the hydrogen outlet are provided with a switch valve, so that the hydrogen storage tank C1 is obtained.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C1, the volume ratio of hydrogen storage is 15.1, and the circulation stability value of hydrogen storage is 100%. Wherein: the volume ratio of hydrogen storage is equal to the volume of hydrogen gas/volume of the organic composite porous ceramic body; when the circulation stability value is 1000 th hydrogen storage, the ratio percentage of hydrogen storage volume to first hydrogen storage volume is defined as circulation stability value ═ VH2,1000/VH2,1*100％。
Example 8: preparation of hydrogen storage tank C2 by organic composite ceramic material
The hydrogen storage tank C2 was produced in the same manner as in the hydrogen storage tank C1 in example 7, and the specific procedure was as in example 7. However, unlike example 7, the porous ceramic precursor used in example 2 was used.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C2, the volume ratio of the hydrogen storage is 19.0, and the circulation stability value of the hydrogen storage is 100%.
Example 9: preparation of hydrogen storage tank C3 by organic composite ceramic material
The hydrogen storage tank C3 was produced in the same manner as in the hydrogen storage tank C1 in example 7, and the specific procedure was as in example 7. However, unlike example 7, the porous ceramic precursor used in example 3 was used.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C3, and the volume ratio of the hydrogen storage is 17.8, and the circulation stability value of the hydrogen storage is 100%.
Example 10: preparation of hydrogen storage tank C4 by organic composite ceramic material
The hydrogen storage tank C4 was produced in the same manner as in the hydrogen storage tank C4 in example 7, and the specific procedure was as in example 7. However, unlike example 7, the porous ceramic precursor used in example 4 was used.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C3, the volume ratio of the hydrogen storage is 21.2, and the circulation stability value of the hydrogen storage is 100%.
From the results of the hydrogen storage capacity test of examples 7 to 10, it can be seen that the organic composite porous ceramic of the present invention has excellent cycle stability, and the higher the porosity, the better the hydrogen storage capacity.
Example 11: preparation of hydrogen storage tank C5 by organic composite ceramic material
The hydrogen storage tank C5 was produced in the same manner as in the hydrogen storage tank C1 in example 7, and the specific procedure was as in example 7. However, the difference from example 7 was that 15g of silica and 57g of diatomaceous earth were contained as components in the porous ceramic precursor.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C5, the volume ratio of the hydrogen storage is 18.8, and the circulation stability value of the hydrogen storage is 100%.
Example 12: preparation of hydrogen storage tank C6 by organic composite ceramic material
The hydrogen storage tank C6 was produced in the same manner as in the hydrogen storage tank C1 in example 7, and the specific procedure was as in example 7. However, unlike example 7, the porous ceramic precursor contained 10g of silica, diatomaceous earth 62.
At 3-5MPa and normal temperature, hydrogen is injected into the hydrogen storage tank C6, the volume ratio of hydrogen storage is 12.5, and the circulation stability value of hydrogen storage is 100%.
From the results of the hydrogen storage capacity test of examples 10 to 12, it can be seen that the organic composite porous ceramic of the present invention has excellent cycle stability, and the hydrogen storage property thereof is a physical change determined by the adsorption capacity of silica and diatomaceous earth. When the content of the silica is increased, the hydrogen storage volume of the organic composite porous ceramic material is increased; when the content of silica is reduced, the hydrogen storage volume of the organic composite porous ceramic material is reduced.
From the above experimental results of the examples and comparative examples, it can be seen that the present invention can improve the porosity of the porous ceramic by the content, change the particle size of the modified cellulose and adjust the pore size of the porous ceramic, so that the pore size distribution of the porous ceramic is uniform. The diatomite and the silicon dioxide have excellent adsorption capacity, improve the hydrogen storage capacity of the hydrogen storage tank, and have large porosity and large hydrogen storage volume.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. The organic composite porous ceramic material is characterized by comprising the following raw materials in parts by mass: 10-15 parts of silicon dioxide, 50-70 parts of diatomite, 5-10 parts of aluminum powder and 15-30 parts of modified cellulose, wherein the preparation method comprises the following steps:
(1) modified cellulose: adding a silane coupling agent into a solvent for dissolving, then adding a proper amount of acetic acid, adjusting the pH value to 4, soaking plant cellulose into the solution at the temperature of 60-80 ℃ for 9-12h, taking out, filtering, drying and ball-milling to obtain modified cellulose, wherein the mass ratio of the plant cellulose to the silane coupling agent is (5-6): 1;
(2) uniformly mixing silicon dioxide, aluminum powder, kieselguhr and modified cellulose, grinding into mixed powder, adding a water-soluble adhesive and water into the mixed powder, uniformly mixing, reacting at 60-80 ℃ for 4-6h, and freeze-drying to obtain a porous ceramic precursor;
(3) loading the porous ceramic precursor into a hot-pressing mold, sintering at high temperature of 500 ℃ in the atmosphere of reducing gas and keeping the temperature for 1-2h to prepare a porous ceramic blank;
(4) and (3) roasting the porous ceramic blank at the temperature of 1000-1200 ℃ by taking nitrogen as protective gas, keeping the temperature for 3-6h, cooling the porous ceramic blank to room temperature along with the furnace, and removing the porous ceramic blank to obtain the organic composite porous ceramic material.
2. The organic porous ceramic material according to claim 1, wherein the modified cellulose has an average particle size of 2 to 4 μm.
3. The organic porous ceramic material according to claim 1, wherein the average particle diameters of the silica and the aluminum powder are each 5 to 8 μm.
4. The organic porous ceramic material according to claim 1, wherein the diatomaceous earth has an average particle size of 10 to 20 μm.
5. The organic composite porous ceramic material according to claim 1, wherein the plant cellulose is prepared by the method of step (1): drying plant straw, pulverizing, hydrolyzing in 75% sulfuric acid solution for 10min, neutralizing with NaOH solution, washing with distilled water to neutrality, and drying.
6. The organic composite porous ceramic material according to claim 1, wherein the mass ratio of the mixed powder, the water-soluble binder and water in the step (2) is 1: (0.02-0.04): (1.2-1.4).
7. The organic composite porous ceramic material as claimed in claim 6, wherein the water soluble binder is one or both of polyvinyl alcohol and carboxymethyl cellulose.
8. The organic composite porous ceramic material according to claim 1, wherein the freeze-drying method in the step (2) is: the freezing is divided into a freezing part and a drying part, the freezing temperature is-40 to-30 ℃, and the freezing time is 2 to 3 hours; the drying temperature is-20-10 ℃, the drying time is 18-24h, and the vacuum degree during the drying period is kept at 7-15 Pa.
9. Use of the organic composite porous ceramic material according to any one of claims 1 to 8 in a hydrogen storage material.
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