CN110193361B - Preparation method of irreversible hydrogen absorption porous composite material and product thereof - Google Patents
Preparation method of irreversible hydrogen absorption porous composite material and product thereof Download PDFInfo
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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Abstract
The invention discloses a preparation method of an irreversible hydrogen absorption porous composite material and a product thereof, wherein the preparation method comprises the following steps: a preparation method of an irreversible hydrogen absorption porous composite material comprises the following steps: 1) mixing the powder hydrogen absorbing agent, the matrix material and the pore-forming agent in proportion to form a mixture, 2) hot-pressing the mixture prepared in the step 1) for forming and cooling, wherein the matrix material and the pore-forming material form a bicontinuous phase in the process; 3) removing the pore-forming agent from the pressed and formed product in the solvent; the matrix material is a water-insoluble and alcohol-insoluble thermoplastic polymer material; the pore-forming agent is a water-soluble or alcohol-soluble polymer material; the powder hydrogen absorbing agent is an unsaturated hydrocarbon-noble metal powder hydrogen absorbing agent which is not water-soluble and alcohol-soluble. The irreversible hydrogen-absorbing porous composite material prepared by the preparation method has the advantages of high hydrogen-absorbing rate, large hydrogen-absorbing capacity and convenience for processing and forming.
Description
Technical Field
The invention relates to the technical field of functional composite materials, in particular to a preparation method of an irreversible hydrogen absorption porous composite material and a product thereof.
Background
The hydrogen is used as a combustible gas, when the volume fraction of the hydrogen in the air reaches 4-75%, the hydrogen can explode when meeting a fire source, and particularly after the explosion of the Japanese Fudao nuclear power station caused by hydrogen accumulation, the safety control of the hydrogen draws more attention; in addition, hydrogen also has extremely strong permeability, and the existence of the hydrogen can cause hydrogen damage to materials and components, so that the structure and the performance of the materials are damaged, and the functions of the components are damaged. Therefore, the hydrogen absorption material is adopted to realize the rapid elimination of hydrogen at room temperature, and the method has important practical significance in the fields of safe production, guarantee of the structure and performance of the material in a closed environment, stability of the functions of components and the like.
The hydrogen absorbing material can be classified into a reversible hydrogen absorbing material and an irreversible hydrogen absorbing material according to whether the absorbed hydrogen can be released again. Reversible hydrogen absorbing materials, also known as hydrogen storage materials, are physical hydrogen absorbing materials, while irreversible hydrogen absorbing materials are chemical hydrogen absorbing materials.
For the irreversible hydrogen-absorbing material, the powder hydrogen-absorbing agent used can be classified into inorganic compound powder hydrogen-absorbing agent and organic compound powder hydrogen-absorbing agent. The irreversible hydrogen absorption material prepared by adopting the inorganic compound as the powder hydrogen absorption agent belongs to the irreversible hydrogen absorption composite material with a compact structure, is convenient for molding and processing, and has the defects of low hydrogen absorption rate, low utilization rate of effective components and the like. In the irreversible hydrogen absorption material prepared by adopting the organic compound as the powder hydrogen absorption agent, the catalytic hydrogenation type organic powder hydrogen absorption agent has the advantages of high hydrogen absorption rate, large hydrogen absorption capacity, irreversible adsorption, capability of still playing a role in common atmospheres such as water vapor and carbon dioxide and the like, and is the most widely applied powder hydrogen absorption agent at present. The powder hydrogen absorbing agent realizes the rapid elimination of hydrogen at normal temperature and pressure by utilizing the addition reaction of unsaturated organic compounds and hydrogen under the action of metal catalysis. Among the existing various organic powder hydrogen absorbents, the most widely used is a composite powder hydrogen absorbent (DEB-Pd/C) of 1, 4-Diphenylethynylbenzene (DEB) and catalyst palladium (Pd) and carbon (C). The existing irreversible hydrogen absorbing material prepared by adopting an organic compound as a powder hydrogen absorbing agent is a powdery organic powder hydrogen absorbing agent, and although the powdery organic powder hydrogen absorbing agent has the advantages of high hydrogen absorbing rate and large hydrogen absorbing capacity, the existing powdery organic hydrogen absorbing agent can be used only by being packaged in a breathable outer package, and the risk of dust pollution, short circuit of components and the like is caused when the package is damaged. Although several existing hydrogen-absorbing agent forming technologies solve the problem of powder forming, the hydrogen-absorbing rate is slow and the hydrogen-absorbing capacity is small.
Disclosure of Invention
The invention aims to provide a preparation method of an irreversible hydrogen-absorbing porous composite material, which can solve the problems that the traditional powdery organic hydrogen-absorbing agent is difficult to process and form, is inflammable and cannot be used in forms of elastomers or films and the like. Meanwhile, the problems of low hydrogen absorption rate and small hydrogen absorption capacity of the irreversible hydrogen absorption composite material with a compact structure can be solved.
In addition, the invention also provides an irreversible hydrogen absorption porous composite material, and the irreversible hydrogen absorption porous composite material prepared by the preparation method has the advantages of high hydrogen absorption rate, large hydrogen absorption capacity and convenience for processing and forming.
The invention is realized by the following technical scheme:
a preparation method of an irreversible hydrogen absorption porous composite material comprises the following steps:
1) mixing the powder hydrogen absorbing agent, the matrix material and the pore-forming agent in proportion to form a mixture,
2) hot-pressing the mixture prepared in the step 1), forming and cooling, wherein a bicontinuous phase is formed by the substrate material and the pore-forming material in the process;
3) removing the pore-forming agent from the pressed and formed product in the solvent;
the matrix material is a water-insoluble and alcohol-insoluble thermoplastic polymer material; the pore-forming agent is a water-soluble or alcohol-soluble polymer material; the powder hydrogen absorbing agent is an unsaturated hydrocarbon-noble metal powder hydrogen absorbing agent which is not water-soluble and alcohol-soluble.
In the prior art, the irreversible hydrogen absorbing material prepared by the prior method is a powdery organic powder hydrogen absorbing agent or an irreversible hydrogen absorbing material with a compact structure.
The preparation method is based on a bicontinuous phase single-phase etching method, the bicontinuous phase refers to two high polymer materials with poor compatibility or complete incompatibility, you are in my of the formed polymer alloy, and the distribution of any one high polymer material in the polymer alloy is continuous. A bicontinuous phase single phase etching method is that on the basis of forming polymer alloy with bicontinuous phase structure, one polymer material is dissolved and removed by a solvent and the other polymer material is completely retained.
The substrate material and the powder hydrogen absorbing agent are completely insoluble in the same solvent capable of dissolving the pore-forming agent, and the compatibility between the substrate material and the pore-forming agent is poor or completely incompatible.
Specifically, the hot press forming and cooling process of the invention is as follows:
hot-pressing the mixed powder by a flat vulcanizing machine, wherein the forming pressure is 5-10MPa, and the forming temperature is higher than the hot processing temperature of the base material and is less than the melting point of organic components in the hydrogen absorbent, namely less than 180 ℃. If the temperature is too low, the base material is not melted and cannot be processed, and if the temperature is too high, the organic components of the hydrogen absorbing agent are melted and segregated, so that the hydrogen absorbing performance is greatly reduced. And cooling by adopting a quick water cooling method to shape the bicontinuous phase.
The preparation method comprises the steps of firstly utilizing a uniform blend of three raw materials of a substrate material, a pore-forming agent and an organic powder hydrogen-absorbing agent in the conventional compression molding process, forming a continuous bicontinuous phase of the substrate material and the pore-forming agent when the ratio of the volume percentage of the pore-forming agent to the volume percentage of the substrate material incompatible with the pore-forming agent is kept within a certain range, and then removing the pore-forming agent by utilizing a proper solvent to prepare the irreversible hydrogen-absorbing porous composite material. The irreversible hydrogen-absorbing porous composite material product prepared by the method has the following advantages: 1) the porous structure is highly communicated, so that the diffusion rate of hydrogen in the hydrogen absorption material can be greatly improved; 2) the hydrogen absorption rate is high, and full adsorption can be achieved within two to three minutes; 3) high hydrogen absorption capacity; 4) good film forming property and high mechanical strength. Compared with the traditional powder hydrogen absorbing agent and the hydrogen absorbing composite material with a compact structure, the hydrogen absorbing porous composite material prepared by the preparation method provided by the invention has very obvious advantages.
Further, the volume percentage of the matrix material and the pore-forming agent is as follows: 70 percent, 30 percent to 50 percent and 50 percent.
The volume percentage of the matrix material and the pore-forming agent is set to 70 percent, 30 percent to 50 percent and 50 percent, so that a bicontinuous phase with continuous matrix material and pore-forming agent can be formed.
Further, the weight percentage of the powder hydrogen absorbing agent accounts for 10-30% of the total weight of the three raw materials.
The larger the proportion of the hydrogen absorbing agent in the porous hydrogen absorbing composite material is, the larger the hydrogen absorbing capacity per unit mass is, and the faster the hydrogen absorbing rate is, but the structural strength and toughness of the porous hydrogen absorbing composite material are reduced, and the mass proportion of the hydrogen absorbing agent powder is set to be 10-30 percent in comprehensive consideration
Further, the matrix material is polyethylene, ethylene-vinyl acetate copolymer or thermoplastic polyurethane.
The polyethylene is Low Density Polyethylene (LDPE) or High Density Polyethylene (HDPE).
Further, the pore-forming agent is polyethylene oxide, polyvinylpyrrolidone, tert-butyl hydroquinone or butyl hydroxy anisol.
The polyoxyethylene and the polyvinylpyrrolidone are water-soluble high polymer materials; the tert-butyl hydroquinone or the butyl hydroxy anisol is an alcohol-soluble high polymer material.
The selection of all the substrate materials and pore-forming materials of the invention has several necessary conditions: firstly, the hot working temperature is lower than the melting point of the effective components in the powder hydrogen absorption agent, otherwise, the forming and hydrogen absorption performances can not be considered. Secondly, the organic components in the hydrogen absorbing agent are selected according to the dissolution characteristics, so that the pore-forming material cannot be dissolved by adopting the solvents with good solubility in halogenated solvents, tetrahydrofuran and other solvents, but the solvents which are insoluble in the organic components of the hydrogen absorbing agent, such as water, alcohols, ethanol and the like, are used as eluting solvents, so that the pore-forming agent can only adopt water-soluble or alcohol-soluble materials, and meanwhile, the substrate material adopts water-insoluble and alcohol-insoluble materials.
Further, the powder hydrogen absorbing agent is 1, 4-diphenylethynylbenzene and palladium carbon, 1, 4-diphenyldiacetylene and palladium carbon or 1,3, 5-triphenylethynylbenzene and palladium carbon.
Further, water is used as a solvent when a water-soluble polymer material is used as the pore-forming agent, and an alcohol such as ethanol is used as a solvent when an alcohol-soluble polymer material is used as the pore-forming agent.
Further, the base material is polyethylene, the pore-forming agent is polyethylene oxide, the powder hydrogen absorbing agent is 1, 4-diphenylethynylbenzene and palladium carbon, the solvent for removing the pore-forming agent is water, the volume percentage of the base material to the pore-forming agent is 70 percent to 30 percent to 50 percent, and the weight percentage of the powder hydrogen absorbing agent accounts for 10 to 30 percent of the total weight of the three raw materials.
An irreversible hydrogen-absorbing porous composite material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the hydrogen absorption porous composite material prepared by adopting the continuous phase single-phase etching method has the advantages of high communication of porous structures, high hydrogen absorption rate (equivalent to the rate of a powder hydrogen absorption agent and far higher than the data of other formed powder hydrogen absorption agents), large hydrogen absorption capacity, good film forming property, certain mechanical property and the like, can completely solve the problems that the traditional powder organic powder hydrogen absorption agent is difficult to process and form, is inflammable, cannot be used in the forms of elastomers or films and the like, cannot realize other functions and the like, and can also solve the problems that the hydrogen absorption rate is low, the utilization rate of effective components is low and the like in the hydrogen absorption composite material with a compact structure.
2. The preparation method is simple, and the raw materials are cheap, easy to obtain and nontoxic.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a scanning electron microscope image of 10 μm of a brittle section of the thin film prepared in example 1;
FIG. 2 is a 200um SEM image of a brittle section of the thin film prepared in example 1;
fig. 3 is a graph comparing the normalized hydrogen absorption of different samples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1:
respectively weighing 44.00g of powdery low-density polyethylene (LDPE), 31.00g of powdery polyethylene oxide (PEO), 25.00g of powdery 1, 4-diphenylethynylbenzene and palladium-carbon (DEB-Pd/C), firstly mixing the LDPE and the PEO to form a bicontinuous phase, then adding the DEB-Pd/C, then uniformly mixing the LDPE and the PEO in a three-dimensional motion mixer, then pressing and molding the uniform blend of the LDPE and the PEO on a flat-plate vulcanizing machine at the conventional plastic processing temperature, then soaking the pressed and molded product in flowing water to remove a pore-forming agent PEO, finally airing the molded product without the pore-forming agent and drying the molded product in a vacuum drying box to constant weight to obtain the film product of the irreversible hydrogen-absorbing porous composite material prepared based on the bicontinuous phase single-phase etching method.
As shown in fig. 1 and fig. 2, the scanning electron microscope observation result of the brittle section of the irreversible hydrogen-absorbing porous composite material film product prepared by the method of the embodiment is shown in fig. 1, and a clear porous structure can be seen.
Example 2:
40.46g of powdery low-density polyethylene (LDPE), 45.54g of powdery Butyl Hydroxy Anisole (BHA), 15.00g of powdery 1, 4-diphenyl butyne and palladium carbon (BPB-Pd/C) are respectively weighed, firstly, the LDPE and the BHA are mixed to form a bicontinuous phase, then DEB-Pd/C is added, then, the three components are uniformly mixed in a three-dimensional motion mixer, then, the uniform mixture of the three components is pressed and formed on a flat vulcanizing machine at the conventional plastic processing temperature, then, a pore-forming agent BHA is removed from the pressed and formed product in an ethanol reflux mode, finally, the formed product with the pore-forming agent removed is dried and dried in a vacuum drying box to constant weight, and then the film product (porous membrane sample) of the irreversible hydrogen-absorbing porous composite material prepared based on the bicontinuous phase single-phase etching method is obtained.
Examples 3 to 10:
examples 3-10 were prepared in a similar manner to examples 1 and 2, except for the raw material composition and content, and the specific differences are shown in table 1.
Comparative example (dense film sample preparation):
respectively weighing 44.00g of powdery low-density polyethylene (LDPE), 25.00g of powdery 1, 4-diphenylethynylbenzene and palladium-carbon (DEB-Pd/C), uniformly mixing the LDPE and the DEB-Pd/C in a three-dimensional motion mixer, then pressing and molding the uniform blend on a flat vulcanizing machine at the conventional plastic processing temperature, and cooling to obtain a compact film sample.
The irreversible hydrogen absorption porous composite material film product (porous film sample) prepared in the example 1, the traditional powdery organic powder hydrogen absorption agent sample (powder sample) and the traditional dense film sample are respectively placed in a hydrogen absorption testing device to test the hydrogen absorption amount and the hydrogen absorption rate. The results show that the porous composite film product and the powder sample reach a hydrogen absorption platform within 150s, and the compact sample absorbs slowly and has small absorption amount. The hydrogen absorption capacity of the porous hydrogen absorption membrane was 4.2 mg/g. In order to compare the hydrogen absorption reaction rates of the three hydrogen absorption materials conveniently, the normalized hydrogen absorption amounts of the three samples are listed in fig. 3, and the hydrogen absorption amount of the final platform of the curve is 100%, so that the hydrogenation reaction conversion rates of different samples are reflected. The hydrogenation conversion rate of the porous hydrogen absorption film is equivalent to that of a powder sample and is far higher than that of a compact film sample.
TABLE 1
In Table 1, LDPE is low density polyethylene, HDPE is high density polyethylene, EVA is ethylene-vinyl acetate copolymer,TPU is thermoplastic polyurethane, PEO is polyethylene oxide, PVP is polyvinylpyrrolidone, TBHQ is tert-butyl hydroquinone, BHA is butyl hydroxy anisole, DEB-Pd/C is 1, 4-diphenylethynylbenzene and palladium carbon, BPB-Pd/C is 1, 4-diphenyldiacetylene and palladium carbon, TEB-Pd/C is 1,3, 5-triphenylethynylbenzene and palladium carbon; v in the tableBase material:VPore-forming agentRepresenting the ratio of the volume percentages of the matrix material and the pore-forming agent in the mixture of the matrix material and the pore-forming agent; the mass percent and the volume percent of the table are converted into the density, and the density is calculated by LDPE (low-density polyethylene) 0.921, HDPE 0.953, EVA 0.948, TPU 1.150, PEO 1.205, PVP 1.144, TBHQ 1.241 and BHA 1.014.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the irreversible hydrogen absorption porous composite material is characterized by comprising the following steps:
1) mixing the powder hydrogen absorbing agent, the matrix material and the pore-forming agent in proportion to form a mixture,
2) hot-pressing the mixture prepared in the step 1), forming and cooling, wherein a bicontinuous phase is formed by the substrate material and the pore-forming material in the process;
3) removing the pore-forming agent from the pressed and formed product in the solvent;
the matrix material is a water-insoluble and alcohol-insoluble thermoplastic polymer material; the pore-forming agent is a water-soluble or alcohol-soluble polymer material; the powder hydrogen absorbing agent is an unsaturated hydrocarbon-precious metal powder hydrogen absorbing agent which is not water-soluble and alcohol-soluble;
the hot-press molding temperature is higher than the hot processing temperature of the base material and is less than the melting point of the organic component in the hydrogen absorbent.
2. The method for preparing the irreversible hydrogen-absorbing porous composite material according to claim 1, wherein the volume percentages of the matrix material and the pore-forming agent are as follows: 70 percent, 30 percent to 50 percent and 50 percent.
3. The method for preparing an irreversible hydrogen-absorbing porous composite material according to claim 1, wherein the weight percentage of the hydrogen-absorbing powder is 10-30% of the total weight of the three raw materials.
4. The method for preparing an irreversible hydrogen-absorbing porous composite material according to claim 1, wherein the matrix material is polyethylene, ethylene-vinyl acetate copolymer or thermoplastic polyurethane.
5. The method for preparing an irreversible hydrogen-absorbing porous composite material according to claim 1, wherein the pore-forming agent is polyethylene oxide, polyvinylpyrrolidone, tert-butylhydroquinone or butyl hydroxy anisole.
6. The method of claim 1, wherein the hydrogen getter powder is 1, 4-diphenylethynylbenzene and palladium-carbon, 1, 4-diphenylbutadiyne and palladium-carbon, or 1,3, 5-triphenylethynylbenzene and palladium-carbon.
7. The method according to claim 1, wherein water is used as a solvent when the water-soluble polymer material is used as the pore-forming agent, and an alcohol such as ethanol is used as a solvent when the alcohol-soluble polymer material is used as the pore-forming agent.
8. The method as claimed in claim 1, wherein the matrix material is polyethylene, the pore-forming agent is polyethylene oxide, the powder hydrogen-absorbing agent is 1, 4-diphenylethynylbenzene and palladium-carbon, the solvent for removing the pore-forming agent is water, the volume percentage of the matrix material to the pore-forming agent is 70%:30% -50%: 50%, and the weight percentage of the powder hydrogen-absorbing agent is 10-30% of the total weight of the three raw materials.
9. An irreversible hydrogen-absorbing porous composite material produced by the production method according to any one of claims 1 to 8.
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