CN112824740A - Inner container of hydrogen storage tank and preparation method thereof - Google Patents

Inner container of hydrogen storage tank and preparation method thereof Download PDF

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Publication number
CN112824740A
CN112824740A CN201911142857.6A CN201911142857A CN112824740A CN 112824740 A CN112824740 A CN 112824740A CN 201911142857 A CN201911142857 A CN 201911142857A CN 112824740 A CN112824740 A CN 112824740A
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barrier layer
nylon
storage tank
hydrogen storage
layer
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刘振国
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0626—Multiple walls
    • F17C2203/0629—Two walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/066—Plastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/068—Special properties of materials for vessel walls
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention provides a hydrogen storage tank liner and a preparation method thereof, belonging to the technical field of storage tanks, wherein the hydrogen storage tank liner comprises an outer layer and a barrier layer, the barrier layer is attached to the inner surface of the outer layer, the barrier layer comprises polyvinyl alcohol and/or polyvinyl alcohol copolymer, and the barrier layer further comprises 0.1-10% of nano montmorillonite in percentage by weight; the inner container of the hydrogen storage tank has better barrier property.

Description

Inner container of hydrogen storage tank and preparation method thereof
Technical Field
The invention relates to the technical field of storage tanks, in particular to an inner container of a hydrogen storage tank and a preparation method thereof.
Background
Hydrogen storage is an important subject in the field of new energy because hydrogen is a molecule with a very small diameter, has higher permeability than oxygen and water vapor, and is easy to explode when being mixed with oxygen, so that compared with a common gas storage tank body, the inner container of the hydrogen storage tank needs a firm outer layer and a compact lining coating to prevent hydrogen leakage and external oxygen from entering, and explosion is prevented from occurring at high temperature after the hydrogen and the oxygen are mixed. Therefore, a hydrogen storage tank liner with good barrier property is needed.
Disclosure of Invention
Therefore, the hydrogen storage tank inner container with better barrier property and the preparation method thereof are needed to be provided.
The invention provides a hydrogen storage tank liner which comprises an outer layer and a barrier layer, wherein the barrier layer is attached to the inner surface and/or the outer surface of the outer layer, and the barrier layer comprises polyvinyl alcohol and/or polyvinyl alcohol copolymer.
Preferably, the barrier layer also comprises 0.1 to 10 percent of nano montmorillonite in percentage by weight; and/or the presence of a gas in the gas,
the barrier layer further comprises 5-10% of a melamine resin, and the polyvinyl alcohol and/or polyvinyl alcohol copolymer is crosslinked by the melamine resin.
Preferably, the outer layer is made of a nylon material; the nylon material comprises the following materials: one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof.
Preferably, the outer layer further comprises 1-10% of a modifying substance by weight percentage, and the modifying substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer.
Preferably, the thickness of the outer layer is 50-5000 μm; and/or the presence of a gas in the gas,
an adhesive layer is arranged between the outer layer and the barrier layer, and the thickness of the adhesive layer is 0-100 mu m; and/or the presence of a gas in the gas,
the thickness of the barrier layer is 2-500 μm.
Preferably, an adhesive layer is further disposed between the outer layer and the barrier layer, and the adhesive layer comprises the following substances: one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid.
Preferably, the nano-montmorillonite is dispersed in the barrier layer;
the grain size of the nano montmorillonite is 0.01-10 mu m; and/or, the content of the nano montmorillonite is 0.1-0.46% or 7-10% by weight percentage.
The invention also provides a hydrogen storage tank liner, which comprises an outer layer and a barrier layer, wherein the barrier layer is attached to the inner surface of the outer layer,
the barrier layer comprises the following substances in percentage by weight: 0.1 to 10 percent of nano montmorillonite, 5 to 10 percent of melamine resin and the balance of polyvinyl alcohol and/or polyvinyl alcohol copolymer; and/or the presence of a gas in the gas,
the outer layer consists of the following substances in percentage by weight: 1-10% of modified substance, wherein the modified substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer, and the balance is nylon material, and the nylon material comprises one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof.
The invention also provides a preparation method of the inner container of the hydrogen storage tank, which comprises the following steps:
1) forming nylon or copolymer thereof into a tank body in a blow molding mode;
2) coating the barrier layer material on the inner surface, and curing in a curing chamber at 35-65 ℃ for 4-6h to form the barrier layer.
10. The method of claim 1, further comprising, after step 1), the steps of: coating solution of one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid as adhesive on the inner surface, and aging in aging chamber at 70-100 deg.C for 40-80 min.
According to the invention, the blocking layer is made of polyvinyl alcohol and/or polyvinyl alcohol copolymer, so that the blocking effect of the inner container of the hydrogen storage tank is better.
Drawings
Fig. 1 is a schematic sectional view showing the inner bladder of a hydrogen storage tank according to a preferred embodiment of the present invention;
fig. 2 is an enlarged view of a portion a in fig. 1.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and can implement the present invention, but the embodiments are not limited to the present invention.
As shown in fig. 1-2, an embodiment of the present invention provides a hydrogen storage tank liner, which includes an outer layer 1 and a barrier layer 3, wherein the barrier layer 3 is attached to an inner surface and/or an outer surface of the outer layer 1, and the barrier layer 3 includes polyvinyl alcohol and/or polyvinyl alcohol copolymer. Because the polyvinyl alcohol and/or polyvinyl alcohol copolymer has better gas blocking effect, the polyvinyl alcohol and/or polyvinyl alcohol copolymer is used as the blocking layer, so that the inner container of the hydrogen storage tank has better blocking effect, the hydrogen leakage is reduced, and the oxygen entering the hydrogen tank is reduced.
In a preferred embodiment, the barrier layer 3 further comprises 0.1-10% by weight of nano-montmorillonite. Specifically, the amount of nano-montmorillonite contained in the barrier layer 3 is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%. The nano montmorillonite is uniformly distributed in the barrier layer 3.
The nano montmorillonite is insoluble in water. The surface of the montmorillonite is provided with negatively charged silicate sheets which are piled together by virtue of the electrostatic action among layers to form an earthy mineral, and a unit cell in the crystal structure of the montmorillonite is formed by sandwiching a layer of aluminum oxygen octahedron between two layers of silicon-oxygen tetrahedrons, so that the montmorillonite has a unique one-dimensional layered nano structure and cation exchange property, and the montmorillonite is endowed with a great modification possibility. The modified nano montmorillonite has strong adsorption capacity, can be widely applied to the high polymer material industry as an additive of a nano polymer high polymer material, and improves the tensile strength, the bending strength and the dimensional stability of the nano polymer high polymer material, thereby playing a role in enhancing the comprehensive physical properties of the polymer and reducing the moisture absorption speed of the material. However, as the content of the nano montmorillonite increases, the hydrogen barrier effect of the barrier layer 3 formed of the polyvinyl alcohol and/or the polyvinyl alcohol copolymer is also deteriorated. This embodiment adopts reasonable proportion's nanometer montmorillonite to add in barrier layer 3, under the condition that does not influence barrier layer 3's separation effect, can also improve barrier layer 3's mechanical properties, weaken barrier layer 3's water absorption effect, makes barrier layer 3's separation effect can keep time longer, and life is longer.
In a preferred embodiment, the barrier layer 3 further comprises 5-10% of melamine resin, and the polyvinyl alcohol and/or polyvinyl alcohol copolymer is crosslinked by the melamine resin. Specifically, the barrier layer 3 further contains 6%, 7%, 8%, or 9% of melamine resin.
The melamine resin is insoluble in cold water, has stable property at normal temperature, can be used as a coating, can also be used as a cross-linking agent of a high molecular polymer, can be used as a cross-linking agent, has the advantages of better hardness and better durability of the high molecular polymer, and can also reduce the water absorption speed of the high molecular polymer. However, as the proportion of melamine resin increases, the hydrogen blocking ability of the barrier layer 3 also decreases. Therefore, the melamine resin with a reasonable proportion can keep the hydrogen-blocking performance of the high molecular polymer in an excellent state, and the hardness, the durability and the water absorption speed of the high molecular polymer can also reach a better state.
In a preferred embodiment, the thickness of the barrier layer 3 is 2-500 μm, in particular the thickness of the barrier layer 3 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, 100, 200, 300 or 400 μm.
In a preferred embodiment, the outer layer 1 is made of a nylon material, which includes the following materials: one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof. MXD6 is a crystalline nylon resin synthesized by Lum et al in the 50 s of the 20 th century from m-xylylenediamine and adipic acid as raw materials by polycondensation.
In a preferred embodiment, the outer layer 1 further comprises 1-10% by weight of a modifying substance, and the modifying substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer. In particular, the outer layer 1 also comprises 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% of a modifying substance.
Polyolefin elastomers offer a number of advantages over some conventional elastomers: excellent weld line strength, good dispersibility, high equivalent addition impact strength and the like, and the toughness of the tank body can be improved by adding the material into the outer layer 1, so that the tear resistance of the tank body is improved. The maleic anhydride can improve the flexibility of the high molecular polymer and increase the toughness of the high molecular polymer. However, too much maleic anhydride also affects the hardness and strength of the high molecular weight polymer. Because the ethylene propylene rubber has no polar substituent in the molecular structure, the molecular cohesive energy is low, and the molecular chain can keep flexibility in a wider range. Therefore, the polyolefin elastomer, the maleic anhydride and the ethylene propylene diene monomer can improve the toughness of the can body, but the hardness and the strength of the can body are reduced along with the increase of the addition amount, and once the hardness and the strength of the can body are reduced, the service performance of the can body is seriously influenced. Therefore, the proper amount of maleic anhydride can enable the hardness, strength and toughness of the outer layer 1 to reach proper states, increase the flexibility of the tank body, avoid the tank body from breaking and ensure that the strength and hardness of the tank body are in a range without influencing the use.
In a preferred embodiment, the thickness of the outer layer 1 is 50-5000 μm. Specifically, the thickness of the outer layer 1 is 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, or 400 μm.
In a preferred embodiment, an adhesive layer is further arranged between the outer layer 1 and the barrier layer 3, and the thickness of the adhesive layer is 0-100 μm. Specifically, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 90 μm.
In a preferred embodiment, the adhesive layer comprises the following: one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid.
In a preferred embodiment, the coating weight of the barrier layer 3 is 0.1 to 7 grams per square meter; and/or the thickness of the barrier layer 3 is 0.01-10 μm. Specifically, the coating weight of the barrier layer 3 is 0.1 g/square meter, 0.2 g/square meter, 0.3 g/square meter, 0.4 g/square meter, 0.5 g/square meter, 0.6 g/square meter, 0.7 g/square meter, 0.8 g/square meter, 0.9 g/square meter, 1 g/square meter, 2 g/square meter, 3 g/square meter, 4/square meter, 5 g/square meter or 6 g/square meter; and/or the thickness of the barrier layer 3 is 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm or 0.9 μm.
In a preferred embodiment, nano montmorillonite is dispersed in the barrier layer 3, and the particle size of the nano montmorillonite is 0.01-10 μm; and the content of the nano montmorillonite is 0.1-0.46% or 7-10% by weight percentage. Specifically, the particle size of the nano-montmorillonite is 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm or 0.9 μm; and the content of the nano montmorillonite is 0.1%, 0.2%, 0.5%, 0.7%, 0.9%, 1%, 2%, 3%, 4%, 8% or 9% by weight percentage.
In another preferred embodiment, nano-montmorillonite is dispersed in the barrier layer 3, and the particle size of nano-montmorillonite is 0.01-10 μm. Specifically, the thickness of the barrier layer 3 is 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm, or 0.9 μm.
In more preferred embodiments, the nano-montmorillonite is present in an amount of 0.1-0.46% or 7-10% by weight. Specifically, the nano-montmorillonite has a particle size of 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm or 0.9 μm.
The invention also provides a hydrogen storage tank liner, which comprises an outer layer 1 and a barrier layer 3, wherein the barrier layer 3 is attached to the inner surface of the outer layer 1, and the barrier layer 3 consists of the following substances in percentage by weight: 0.1 to 10 percent of nano montmorillonite, 5 to 10 percent of melamine resin, and the balance of polyvinyl alcohol and/or polyvinyl alcohol copolymer and inevitable impurities. The outer layer 1 consists of the following substances in percentage by weight: 10% of modified substance, the modified substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer, and the balance is nylon material; the nylon material comprises one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof, and inevitable impurities.
The embodiment of the invention also provides a hydrogen storage tank liner, which comprises an outer layer 1 and a barrier layer 3, wherein the barrier layer 3 is attached to the inner surface of the outer layer 1, and the barrier layer 3 consists of the following substances in percentage by weight: 0.1 to 10 percent of nano montmorillonite, 5 to 10 percent of melamine resin, and the balance of polyvinyl alcohol and/or polyvinyl alcohol copolymer and inevitable impurities.
The embodiment of the invention also provides a hydrogen storage tank liner, which comprises an outer layer 1 and a barrier layer 3, wherein the barrier layer 3 is attached to the inner surface of the outer layer 1, and the outer layer 1 consists of the following substances in percentage by weight: 1-10% of modified substance, the modified substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer, the balance is nylon material, one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof, and inevitable impurities.
The embodiment of the invention also provides a preparation method of the inner container of the hydrogen storage tank, which comprises the following steps:
1) blow molding the or copolymer thereof into a can body; wherein the nylon is one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof.
2) Coating the barrier layer 3 material on the inner surface to form the barrier layer 3, wherein the barrier layer 3 comprises polyvinyl alcohol and/or polyvinyl alcohol copolymer, the barrier layer 3 also comprises 0.1-10% of nano montmorillonite (by weight percentage), and curing for 4-6h in a curing chamber at 35-65 ℃. Specifically, the amount of nano-montmorillonite contained in the barrier layer 3 is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%. The nano montmorillonite is uniformly distributed in the barrier layer 3. Preferably, the temperature of the curing chamber is 45 ℃ and the curing time is 5 h.
In a preferred embodiment, after the step 1), the following steps are further included: coating solution formed by one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid on the inner surface as an adhesive, curing the coated solution in a curing chamber at 70-100 ℃ for 40-80min, and then performing the step 2). Preferably, the curing temperature is 80 ℃ and the curing temperature is 60 min.
In a preferred embodiment, the barrier layer 3 further comprises 5-10% of melamine resin, and the polyvinyl alcohol and/or polyvinyl alcohol copolymer is crosslinked by the melamine resin. Specifically, the barrier layer 3 further contains 6%, 7%, 8%, or 9% of melamine resin.
In a preferred embodiment, the thickness of the barrier layer 3 is 2-500 μm, in particular the thickness of the barrier layer 3 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, 100, 200, 300 or 400 μm.
In a preferred embodiment, the thickness of the outer layer 1 is 50-5000 μm. Specifically, the thickness of the outer layer 1 is 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, or 400 μm.
In a preferred embodiment, an adhesive layer is further arranged between the outer layer 1 and the barrier layer 3, and the thickness of the adhesive layer is 0-100 μm. Specifically, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 90 μm. The solid content of the bonding layer 2 is 8-15%.
In a preferred embodiment, the coating weight of the barrier layer 3 is 0.1 to 7 grams per square meter; and/or the thickness of the barrier layer 3 is 0.01-10 μm. Specifically, the coating weight of the barrier layer 3 is 0.1 g/square meter, 0.2 g/square meter, 0.3 g/square meter, 0.4 g/square meter, 0.5 g/square meter, 0.6 g/square meter, 0.7 g/square meter, 0.8 g/square meter, 0.9 g/square meter, 1 g/square meter, 2 g/square meter, 3 g/square meter, 4/square meter, 5 g/square meter or 6 g/square meter; and/or the thickness of the barrier layer 3 is 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm or 0.9 μm.
In a preferred embodiment, nano montmorillonite is dispersed in the barrier layer 3, and the particle size of the nano montmorillonite is 0.01-10 μm; and the content of the nano montmorillonite is 0.1-0.46% or 7-10% by weight percentage. Specifically, the particle size of the nano-montmorillonite is 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.09 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm or 0.9 μm; and the content of the nano montmorillonite is 0.1%, 0.2%, 0.5%, 0.7%, 0.9%, 1%, 2%, 3%, 4%, 8% or 9% by weight percentage.
Example one
The utility model provides a hydrogen storage tank inner bag, includes outer 1, tie coat 2 and barrier layer 3, and tie coat 2 is attached in outer 1 internal surface, and tie coat 2 coating is on the surface of tie coat 2, and wherein, barrier layer 3 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 2% modified material; wherein the modified substance comprises 50 percent of polyolefin elastomer, 25 percent of maleic anhydride and 25 percent of ethylene propylene diene monomer (by weight). The bonding layer 2 is made of the following components: polyethylene glycol solution with solid content of 12%. The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) having a solid content of 8%, wherein the polyvinyl alcohol contains 2% by weight of montmorillonite having a diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); coating the inner surface of the outer layer 1 with a polyethylene glycol solution with a solid content of 12%, and curing the can body in a curing chamber at 80 ℃ for 60 min; and finally, coating the barrier layer 3 on the inner surface, wherein the coating weight of the barrier layer 3 is 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a first hydrogen storage tank liner sample.
Example two
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 2% modified material; wherein the modifying substance comprises 50% of polyolefin elastomer, 50% of maleic anhydride (by weight). The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) with a solid content of 8%, wherein the polyvinyl alcohol contains 0.1% of montmorillonite (by weight) with the diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); and then coating the inner surface of the outer layer 1 with a barrier layer 3 at a coating weight of 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a second sample of the inner container of the hydrogen storage tank.
EXAMPLE III
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 2% modified material; wherein the modifying substance comprises 50 percent of maleic anhydride and 25 percent of ethylene propylene diene monomer (by weight). The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) having a solid content of 8%, wherein the polyvinyl alcohol contains 2% by weight of montmorillonite having a diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); then coating the inner surface of the outer layer 1 with a barrier layer 3, wherein the coating weight is 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a third sample of the inner container of the hydrogen storage tank.
Example four
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 10% modified material; wherein the modified substance comprises 50 percent of polyolefin elastomer, 25 percent of maleic anhydride and 25 percent of ethylene propylene diene monomer (by weight). The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) with a solid content of 8%, wherein the polyvinyl alcohol contains 10% of montmorillonite (by weight) with the diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); then coating the inner surface of the outer layer 1 with a barrier layer 3, wherein the coating weight is 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a hydrogen storage tank liner sample IV.
EXAMPLE five
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 2% modified material; wherein the modifying material is a polyolefin elastomer. The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) having a solid content of 8% and containing 2% by weight of montmorillonite having a diameter of 1 μm and 5% by weight of melamine resin. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); and then coating the inner surface of the outer layer 1 with a barrier layer 3 at a coating weight of 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a fifth sample of the inner container of the hydrogen storage tank.
EXAMPLE six
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 10% modified material; wherein the modified substance is ethylene propylene diene monomer. The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) with a solid content of 8%, wherein the polyvinyl alcohol contains 10% of montmorillonite (by weight) with the diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); then coating the inner surface of the outer layer 1 with a barrier layer 3, wherein the coating weight is 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a hydrogen storage tank liner sample six.
Comparative example 1
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2:1), 2% modified material; wherein the modified substance comprises 50 percent of polyolefin elastomer, 25 percent of maleic anhydride and 25 percent of ethylene propylene diene monomer (by weight). The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) having a solid content of 8%. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); and then coating the inner surface of the outer layer 1 with a barrier layer 3 at a coating weight of 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a first inner container comparison sample of the hydrogen storage tank.
Comparative example No. two
The utility model provides a hydrogen storage tank inner bag, includes outer 1 and barrier layer 3, and the attached internal surface in outer 1 of barrier layer 3, wherein, outer 1 is made by following component: nylon 66 and nylon 1212 copolymer (monomer ratio 2: 1). The barrier layer 3 is made of the following components: an aqueous polyvinyl alcohol solution (molecular weight 22000) with a solid content of 8%, wherein the polyvinyl alcohol contains 12% of montmorillonite (by weight) with the diameter of 1 μm. Forming an outer layer 1 by blowing nylon 66 and a nylon 1212 copolymer (monomer ratio of 2: 1); and then coating the inner surface of the outer layer 1 with a barrier layer 3 at a coating weight of 1 g/square meter, and curing for 5 hours in a curing chamber at 45 ℃ after coating to obtain a second inner container comparison sample of the hydrogen storage tank.
And (3) testing barrier property: and testing the first sample, the second sample, the third sample, the fourth sample, the fifth sample, the sixth sample, the first comparison sample and the second comparison sample for multiple times according to the ISO 62 testing standard, wherein the testing time is the first testing, the testing after one year and the testing after two years.
Results of the experiment
Figure BDA0002281422540000101
Figure BDA0002281422540000111
Observing the table above, it can be concluded from the hydrogen permeability coefficients of the first, second, third, fourth and first comparative examples, and the data of the first and second years later that a proper amount of montmorillonite is added to the polyvinyl alcohol and/or polyvinyl alcohol copolymer to enhance the barrier ability of the barrier layer 3, and also to reduce the water absorption rate and improve the anti-aging ability. By comparing the first sample, the second sample and the comparison sample, it can be shown that the addition of the tie layer 2 between the barrier layer 3 and the outer layer 1 can improve the hydrogen barrier capability of the barrier layer 3. By comparing sample five with sample six with the comparison sample, it can be seen that the addition of a suitable amount of melamine resin to polyvinyl alcohol and/or polyvinyl alcohol copolymer can also improve the hydrogen gas barrier ability and the anti-aging ability.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. The inner container of the hydrogen storage tank is characterized by comprising an outer layer and a barrier layer, wherein the barrier layer is attached to the inner surface and/or the outer surface of the outer layer, and the barrier layer comprises polyvinyl alcohol and/or polyvinyl alcohol copolymer.
2. The inner container of a hydrogen storage tank as claimed in claim 1, wherein the barrier layer further comprises 0.1-10% by weight of nano montmorillonite; and/or the presence of a gas in the gas,
the barrier layer further comprises 5-10% of a melamine resin, and the polyvinyl alcohol and/or polyvinyl alcohol copolymer is crosslinked by the melamine resin.
3. The hydrogen storage tank liner of claim 1 wherein said outer layer is made of nylon material; the nylon material comprises the following materials: one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof.
4. The inner container of the hydrogen storage tank of claim 3, wherein the outer layer further comprises 1-10% by weight of a modifying substance, and the modifying substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer.
5. The hydrogen storage tank liner according to claim 1, wherein the outer layer has a thickness of 50 to 5000 μm; and/or the presence of a gas in the gas,
an adhesive layer is arranged between the outer layer and the barrier layer, and the thickness of the adhesive layer is 0-100 mu m; and/or the presence of a gas in the gas,
the thickness of the barrier layer is 2-500 μm.
6. The hydrogen storage tank liner of claim 1 wherein an adhesive layer is further disposed between the outer layer and the barrier layer, the adhesive layer comprising: one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid.
7. The hydrogen storage tank liner of claim 2, wherein said nano-montmorillonite is dispersed within said barrier layer;
the grain size of the nano montmorillonite is 0.01-10 mu m; and/or, the content of the nano montmorillonite is 0.1-0.46% or 7-10% by weight percentage.
8. A hydrogen storage tank liner comprises an outer layer and a barrier layer, wherein the barrier layer is attached to the inner surface of the outer layer,
the barrier layer comprises the following substances in percentage by weight: 0.1 to 10 percent of nano montmorillonite, 5 to 10 percent of melamine resin and the balance of polyvinyl alcohol and/or polyvinyl alcohol copolymer; and/or the presence of a gas in the gas,
the outer layer consists of the following substances in percentage by weight: 1% -10% of modified substance, wherein the modified substance is composed of one or more of polyolefin elastomer, maleic anhydride and ethylene propylene diene monomer, and the balance is nylon material; the nylon material comprises one or more of nylon 6, nylon 66, aromatic nylon MXD6, aromatic nylon MXD8, aromatic nylon MXD10, aromatic nylon 6I/6T or aromatic nylon 6T/6I or copolymer thereof.
9. A preparation method of an inner container of a hydrogen storage tank is characterized by comprising the following steps:
1) forming nylon or copolymer thereof into a tank body in a blow molding mode;
2) coating the barrier layer material on the inner surface, and curing in a curing chamber at 35-65 ℃ for 4-6h to form the barrier layer.
10. The method of claim 1, further comprising, after step 1), the steps of: coating solution of one or more of polyethylene glycol, polyvinyl butyral and polyacrylic acid as adhesive on the inner surface, and aging in aging chamber at 70-100 deg.C for 40-80 min.
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