CN-121991426-A - Material special for liner of hydrogen storage bottle and preparation method and application thereof

Abstract

The invention discloses a material special for a liner of a hydrogen storage bottle, and a preparation method and application thereof, wherein the material special for the liner of the hydrogen storage bottle is prepared from the following raw materials, by weight, 99.67-99.84 parts of ethylene-butylene copolymer polyethylene base resin, 0.05-0.1 part of a main antioxidant, 0.05-0.1 part of an auxiliary antioxidant, 0.05-0.1 part of an acid absorber and 0.01-0.03 part of a nucleating agent. The special material for the liner of the hydrogen storage bottle has excellent hot-melt welding performance, gas barrier performance and pressure resistance.

Inventors

• ZHANG LIYANG
• WANG FAN
• GAO KEJING
• ZHU WENQIN
• ZHU KAIGE
• ZHOU JINGSHENG
• WANG YISEN
• LI SHUANHONG
• ZHANG YUJIAN
• ZHANG FENGBO

Assignees

• 中国石油集团石油化工研究院有限公司
• 中国石油天然气集团有限公司

Dates

Publication Date

20260508

Application Date

20241107

Claims (13)

1. 1. The special material for the liner of the hydrogen storage bottle is characterized by being prepared from the following raw materials in parts by weight:
2. 2. The hydrogen storage bottle liner special material according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight of the ethylene-butene copolymer polyethylene base resin is 8-15, and/or the density of the ethylene-butene copolymer polyethylene base resin is 0.952g/cm 3 ～0.957g/cm 3 .
3. 3. The hydrogen storage bottle liner special material according to claim 1, wherein the ethylene-butylene copolymer polyethylene base resin is obtained by the following method: Enabling a first part of ethylene to enter a first reactor, and performing a first polymerization reaction under the action of a titanium catalyst to generate polyethylene with a melt flow rate of 150g/10 min-200 g/10 min; and transferring the materials in the first reactor to a second reactor, and adding monomer raw materials containing a second part of ethylene into the second reactor to enable the materials in the second reactor to carry out a second polymerization reaction to generate the ethylene-butene copolymer polyethylene base resin with the melt flow rate of 0.7g/10 min-1.4 g/10 min.
4. 4. The hydrogen storage bottle liner special material according to claim 3, wherein the mass of the first portion of ethylene accounts for 48% -52% of the sum of the mass of the first portion of ethylene and the mass of the second portion of ethylene.
5. 5. The hydrogen storage bottle liner special material according to claim 3, wherein the monomer raw material further comprises butene.
6. 6. The hydrogen storage bottle liner specialty feed according to claim 3, wherein the first polymerization reaction is performed in the presence of hydrogen and/or the second polymerization reaction is performed in the presence of hydrogen.
7. 7. The hydrogen storage bottle liner special material according to claim 3, wherein the first polymerization reaction condition is that the temperature is 75-87 ℃ and the pressure is 0.4-0.5 MPa, and/or the second polymerization reaction condition is that the temperature is 75-87 ℃ and the pressure is 0.15-0.5 MPa.
8. 8. The hydrogen storage bottle liner special material according to claim 3, wherein the titanium-based catalyst comprises a main catalyst and a cocatalyst, wherein, The main catalyst is prepared by compounding a magnesium compound, fatty alcohol, an organosilicon compound and titanium halide according to the molar ratio of 1:0.5-30:0.01-5:1-30, wherein the organosilicon compound comprises tetraalkoxysilane with the structure shown in the following formula 1: wherein R 2 、R 3 、R 4 、R 5 is each independently selected from C1-C15 alkyl, C3-C20 cycloalkyl, or C6-C30 aryl; the cocatalyst comprises an organic aluminum compound with a general formula of AlR ' n X 3-n , wherein R' is hydrogen or C1-C20 alkyl, X is halogen, and 1<n is less than or equal to 3; Preferably, the cocatalyst comprises at least one of triethylaluminum (AlEt 3 ), triisobutylaluminum (Al (iso-Bu) 3 ), tri-n-hexylaluminum (Al (n-C 6 H 13 ) 3 ), tri-n-octylaluminum (Al (n-C 8 H 17 ) 3 ), diethylaluminum chloride (AlEt 2 Cl), preferably triethylaluminum or triisobutylaluminum; preferably, the molar ratio of the cocatalyst to titanium in the main catalyst is (1-500): 1.
9. 9. The hydrogen storage bottle liner special material according to claim 8, wherein the main antioxidant is a phenolic antioxidant, the auxiliary antioxidant is a phosphite antioxidant, the acid absorber is a stearic acid absorber, and the nucleating agent is a beta nucleating agent.
10. 10. The hydrogen storage bottle liner special material according to claim 1, wherein the primary antioxidant is 1076, the auxiliary antioxidant is 168, the acid absorber is zinc stearate, and the nucleating agent is 210M.
11. 11. A preparation method of the special material for the liner of the hydrogen storage bottle, which is characterized by comprising the following steps of uniformly mixing ethylene-butylene copolymer polyethylene base resin, a main antioxidant, an auxiliary antioxidant, an acid absorber and a nucleating agent according to the weight ratio, adding the mixture into an extrusion granulator, extruding, cutting small particles into cold water, and drying to obtain the special material for the liner of the hydrogen storage bottle.
12. 12. The method for preparing the material for the hydrogen storage bottle liner according to claim 11, wherein the barrel temperature of the extrusion granulator is 260-270 ℃ and the temperature of the granular cooling water is 60-65 ℃.
13. 13. A preparation method of the hydrogen storage bottle liner is characterized by comprising the steps of injection molding the special material for the hydrogen storage bottle liner according to any one of claims 1-10 to form an end piece of the hydrogen storage bottle liner, extruding the end piece to form the middle section of the hydrogen storage bottle liner, and welding a pair of end pieces and the middle section to form the plastic liner of the hydrogen storage bottle.

Description

Material special for liner of hydrogen storage bottle and preparation method and application thereof Technical Field The invention belongs to the technical field of new energy and renewable energy sources and hydrogen storage bottles, and particularly relates to a special material for a plastic liner of a high-pressure gas hydrogen storage bottle, and a preparation method and application thereof. Background High pressure gaseous hydrogen storage technology is currently the most commonly used hydrogen storage technology, which uses high pressure to compress hydrogen into a high pressure resistant vessel. The high-pressure gaseous hydrogen storage bottle is developed from a steel hydrogen storage container and a metal lining fiber winding reinforced hydrogen storage container to a full composite fiber winding hydrogen storage container, and the aim of reducing the volume weight by reducing the weight of the container and improving the working pressure of the container to improve the hydrogen storage density is continuously pursued, so that the requirement of industrial development is met. Because the high-pressure gaseous hydrogen storage container is a pure steel metal bottle (I-type bottle) and a steel liner fiber winding bottle (II-type bottle) with low hydrogen storage density and poor safety performance, the vehicle-mounted hydrogen storage density requirement is difficult to meet, and the aluminum liner fiber winding bottle (III-type bottle) and the plastic liner fiber winding bottle (IV-type bottle) are composed of the liner, the carbon fiber reinforced resin layer and the glass fiber reinforced resin layer, the quality of the gas bottle is obviously reduced, and the hydrogen storage density per unit mass is improved. Therefore, the vehicle-mounted hydrogen storage bottle mostly uses two types of containers of type III and type IV. The III-type bottle takes forging aluminum alloy as an inner container, and is externally coated with carbon fiber, and the using pressure mainly comprises 35MPa and 70MPa. The IV type bottle takes plastic as an inner container, and carbon fiber is coated outside the inner container, and the using pressure is 70MPa. The metal and the hydrogen can generate hydrogen embrittlement reaction, and compared with metal plastics, the metal plastics are not easy to fatigue and lose efficacy, so compared with a III type hydrogen storage bottle, the IV type bottle has longer fatigue life and better safety performance. The plastic liner of the IV-type bottle can be made of polyethylene or polyamide, and the main raw material of the winding layer is carbon fiber, so that the domestic liner material and the carbon fiber can not meet the requirements of the hydrogen storage bottle for the vehicle due to late development and start, poor raw material performance and the like, and the winding layer mainly depends on import. CN201911412792.2 discloses a plastic liner of a high-pressure hydrogen storage bottle and a preparation method thereof, wherein the liner comprises an outer layer, an outer transition layer, a barrier layer, an inner transition layer and an inner layer from outside to inside. The material of the outer layer is any one or more of polyamide, polyester and high-density polyethylene, the material of the barrier layer is ethylene-vinyl alcohol copolymer or a modified product thereof, the material of the inner layer is any one or more of polyamide, polyester and high-density polyethylene, the outer transition layer is a mixture of the material of the outer layer and the ethylene-vinyl alcohol copolymer, and the inner transition layer is a mixture of the material of the inner layer and the ethylene-vinyl alcohol copolymer. JP2010276146a discloses a high-pressure hydrogen storage bottle whose inner liner is mainly made of a resin (e.g., nylon) having gas barrier properties, and further contains an elastomer additive having hydrogen adsorption properties. Wherein the elastomer improves the tensile properties of the resin liner and inhibits permeation of hydrogen through the elastomer itself by hydrogen adsorption properties to enhance permeation of hydrogen through the entire resin liner. The resin liner material is in a sea-island phase separation structure, the continuous phase is nylon, and the sea-island phase is an elastomer containing a hydrogen absorbing material. In addition, a compatible material is also mixed on the boundary surface of the nylon and the elastomer. The elastomer and the hydrogen absorbent do not enter the nylon and exist in scattered points. CN117430943a discloses an ultrahigh hydrogen barrier nylon-based composite material for a hydrogen storage bottle and a preparation method thereof, wherein the ultrahigh hydrogen barrier nylon-based composite material for the hydrogen storage bottle is prepared into a composite adhesive film by modifying nylon, a crosslinking additive, polystyrene, polypropylene and an auxiliary additive according to the dosage ratio of