CN112662013A - ZSM-5 molecular sieve and mesoporous treatment method and application thereof - Google Patents
ZSM-5 molecular sieve and mesoporous treatment method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of molecular sieve performance optimization, and particularly relates to a ZSM-5 molecular sieve and a mesoporous treatment method and application thereof; the ion exchange capacity of the microporous ZSM-5 molecular sieve is greatly improved by carrying out mesoporous treatment on the microporous ZSM-5 molecular sieve at normal temperature and normal pressure, the pore passage suitable for silver ions to enter is more than 96 percent, and the silver carrying capacity can reach 43.36WT percent at most, which is about 2 percent higher than the silver carrying capacity of the commonly used silver carrying NaY type zeolite molecular sieve, the antibacterial effect is obviously improved, after the silver carrying capacity is added into a high molecular modified material, the antibacterial effect of Ag can be greatly exerted, and the problems of the durability of the silver series antibacterial material and the odor of the high molecular material are solved.
Description
Technical Field
The invention belongs to the technical field of molecular sieve performance optimization, and particularly relates to a ZSM-5 molecular sieve, and a mesoporous treatment method and application thereof.
Background
ZSM-5 zeolite is a new zeolite molecular sieve containing organic amine cation synthesized by Mobil corporation in the end of sixty years in the last century. Because of its many uniqueness in chemical composition, crystal structure and physical and chemical properties, it is mainly used in the preparation of catalyst, especially as hydrocarbon cracking catalyst, and because of its high thermal stability, it can withstand the high temperature of regenerating catalyst. The zeolite molecular sieve is used as a catalyst, only molecules smaller than crystal pores can come in and go out, the catalytic reaction is controlled by the size of the crystal pores of the zeolite, and the zeolite catalyst shows great selectivity to the size and the shape of the molecules of reactants and products. The pore channel system formed by the ZSM-5 zeolite ten-membered ring has the diameter of the medium-sized pore opening, so that the zeolite has good shape selectivity.
Along with the improvement of living standards and the enhancement of health consciousness of people, the demand of various low-odor antibacterial material products is continuously increased, the low-odor antibacterial plastic products account for a great proportion, various living goods such as refrigerators, air conditioners, washing machines, product toys, dust collectors and the like all use various thermoplastic low-odor antibacterial plastics including antibacterial Polyethylene (PE), antibacterial polypropylene (PP), antibacterial Polystyrene (PS) and the like, particularly, in the air intake system of an automobile, water vapor and dust in the atmosphere are attached to the inner wall of a pipeline in the air intake process, mould is easily generated in the humid environment, the harm to human bodies is great, the requirement on the mildew-proof antibacterial effect of the air intake pipeline is required to reduce the harm to the human bodies, the antibacterial Polyethylene (PE) is mostly adopted in the air intake system pipeline, the antibacterial Polystyrene (PS) is mostly adopted in the components in the refrigerator, and the harm to the human bodies is great when the odor of the products is strong, and is unacceptable, so the requirement of low odor of the material is strict. Nowadays, the preparation of low-odor antibacterial plastics is realized by directly adding a certain amount of antibacterial agent and adsorbent in the plastic granulation process, and the preparation method of the antibacterial agent is the key of the antibacterial efficiency. The antibacterial agents are in various types, including inorganic antibacterial agents and organic antibacterial agents, wherein the inorganic antibacterial agents include Ag, Zn-zeolite, Ag, Zn-zirconium phosphate, Ag, Zn-water-soluble glass and the like, and the organic antibacterial agents include quaternary ammonium salts, quaternary phosphonium salts, imidazoles, pyridines, organic metals and the like. Inorganic antibacterial agents and organic antibacterial agents have advantages and disadvantages, and the inorganic antibacterial agents are divided into two major classes, namely antibacterial metal ions, such as silver ions, zinc ions, copper ions and the like, wherein the antibacterial property of the silver ions is strongest. Another class is inorganic metal oxides such as zinc oxide, titanium dioxide, and the like. The inorganic antibacterial agent has high heat resistance, but has the defect that the Ag antibacterial agent is easy to discolor, and has relatively large dosage and high cost; the organic antibacterial agent has the defects of high sterilization efficiency, small addition amount, poor heat resistance, easy precipitation, low safety and the like. With the change of the use environment of plastics or rubber, and the precipitation of the antibacterial agent after soaking in water or frequent contact with water, the antibacterial efficiency will be reduced or even disappeared, so that the antibacterial agent is required to have strong weather resistance and long time.
The development and application of antimicrobial polyethylene can be broadly divided into two categories: one is to physically blend the antimicrobial agent in the polyethylene PE resin. Such as: the invention patent with application number CN96106369.6 discloses a preparation method of a long-acting rapid antibacterial polyethylene product, which adopts silica gel, zeolite, titanium dioxide and alumina as carriers of antibacterial metal salts, low-molecular polyethylene wax as a dispersing agent of an antibacterial agent, and calcium chloride or calcium carbonate is added into polyethylene raw materials to prevent the polyethylene from yellowing and discoloring. The preparation and antibacterial performance of the high molecular quaternary ammonium salt type antibacterial plastic reported in 2007, volume 21, No. 4, is that the high molecular quaternary ammonium salt is grafted on the surface of the nano SiO2 powder by adopting a covalent bonding method to prepare the antibacterial master batch, and the antibacterial master batch is added into polyethylene to prepare the antibacterial plastic. Another type is to bond the antimicrobial agent to the surface of the polyethylene PE article. Such as: patent JP2001340280, the invention is to graft chloromethyl styrene on polyethylene fiber, then to generate quaternary ammonium salt group through quaternization reaction with trimethyl tertiary amine, to prepare polyethylene fiber with antibacterial property. The antibacterial agent is bonded on the surface of the product, so that the antibacterial effect is good in a short period, but the antibacterial effect is gradually weakened along with the time, and the antibacterial time is short.
At present, some technologies utilize the microporous structure of zeolite molecular sieves as a carrier to load metal ions thereon and then prepare bacteriostatic plastics so as to achieve the purposes of bacteriostasis and odor adsorption. Such as: patent document CN201710539810.8 discloses a composite antibacterial film and a preparation method thereof, wherein the composite antibacterial film is prepared from low-density polyethylene, a silver ion antibacterial agent, a nano ZSM-5 molecular sieve, a micron ZSM-5 molecular sieve, a lubricant and a composite stabilizer, and has the functions of preventing dust, inhibiting bacteria and removing ethylene. Patent document No. CN201810975160.6 discloses a bacteriostatic plastic for automotive interior parts and a preparation method thereof, wherein the raw materials include PP resin, POE plastic, HDPE resin, zeolite molecular sieve, activated alumina, nano zinc oxide, and nano silver, and the nano zinc oxide and nano silver are contained in micropores of the zeolite molecular sieve and the activated alumina, so that the plastic has antibacterial property and can adsorb odor of the automotive interior parts. However, in the methods of the above patent documents, zeolite molecular sieves are used as raw materials, and for ZSM-5 molecular sieves, the crystal structure thereof belongs to an orthorhombic system, and has a special structure, and the pore channels are cavities thereof, unlike a cage-like structure such as a-type, X-type and Y-type zeolites, and a general framework is composed of two crossed pore channel systems, so that the crystal structure of ZSM-5 molecular sieves is very stable, but the pore diameter of microporous ZSM-5 molecular sieves is small, generally 0.3 to 2.0nm, water or large ions are difficult to enter, and the amount of silver ions such as silver nitrate entering the pore channels is limited. Therefore, the effect of directly applying it as a carrier is not ideal.
In the prior art, the synthesis of the ZSM-5 molecular sieve is mostly directly carried out, and the molecular sieves obtained by different methods have different structural properties. Such as: the industrial catalysis of the 'seed crystal method for synthesizing the integral porous ZSM-5 molecular sieve' reported in 6 th phase of volume 27 of 2019, 6 th month is characterized in that a synthetic solution is prepared from tetraethoxysilane, aluminum isopropoxide, tetrapropylammonium hydroxide, potassium hydroxide and water, CTAB and Silicalite-1 seed crystal gel are added, and the ZSM-5 molecular sieve is synthesized by a hydrothermal crystallization method. The pore-expanding treatment method aiming at the ZSM-5 molecular sieve is relatively few, the prior art needs to be carried out under the conditions of high temperature and high pressure, or the process conditions in the modification process are not easy to control. The ' influence of tetraethylammonium hydroxide post-crystallization treatment on a ZSM-5 molecular sieve structure and the catalytic performance of methanol to propylene ' reported in volume 34, volume 4 of 7, 7 and 8 in 2018 in Petroleum institute (Petroleum processing) ' is to perform post-crystallization treatment on a high-silicon ZSM-5 molecular sieve synthesized by using tetrapropylammonium hydroxide as a template by using a tetraethylammonium hydroxide solution to prepare the intragranular expanded hierarchical pore ZSM-5 molecular sieve. The post-crystallization treatment of the high-silicon ZSM-5 molecular sieve is carried out by adopting tetraethyl ammonium hydroxide solution at the temperature of 170 ℃ by adopting a high-pressure crystallization kettle.
In summary, it is desirable to provide a method for modifying a ZSM-5 molecular sieve that is simple, fast, easy to operate, and consumes less energy, so as to improve the ion exchange capacity of the molecular sieve and further improve the loading capacity of the molecular sieve when the molecular sieve is used as a carrier.
Disclosure of Invention
The invention provides a ZSM-5 molecular sieve and a mesoporous treatment method and application thereof to solve the problems.
The method is realized by the following technical scheme:
the application of the mesoporous ZSM-5 molecular sieve in the preparation of the low-odor antibacterial polyethylene material is characterized in that the microporous ZSM-5 molecular sieve is subjected to mesoporous treatment and then used as a carrier to prepare a self-made silver-carrying molecular sieve, and the self-made silver-carrying molecular sieve is used as one of raw materials for preparing the low-odor antibacterial polyethylene material.
Further, the mesoporous treatment is obtained by carrying out ammonification treatment on the ZSM-5 molecular sieve under the conditions of normal temperature and normal pressure, and comprises the following specific steps:
uniformly stirring the microporous ZSM-5 molecular sieve in 2-3.5mol/L sodium hydroxide solution, soaking for 2 hours, filtering, pumping, washing to obtain a filter cake 1, putting the filter cake 1 into 1-1.5mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, pumping to obtain a filter cake 2, and obtaining the wet ZSM-5 molecular sieve with the particle size of 5-10 mu m and the pore size of 5-50 nm.
Further, the preparation method of the self-made silver-carrying molecular sieve comprises the following steps: and soaking the obtained wet ZSM-5 molecular sieve filter cake in 4mol/L silver nitrate solution for 2 hours, taking out, draining, drying in a microwave drying oven at the temperature of 40 ℃ for 30-35 minutes to obtain an unshaped self-made silver-carrying molecular sieve, calcining, shaping, taking out, cooling, sealing and packaging to obtain the ZSM-5 self-made silver-carrying molecular sieve.
Further, the calcination and the shaping are to place the unshaped self-made silver-carrying molecular sieve in a muffle furnace, dry the unshaped self-made silver-carrying molecular sieve at 200 ℃ for 30-35 minutes, then gradually heat the unshaped self-made silver-carrying molecular sieve to 320-330 ℃ and calcine the unshaped self-made silver-carrying molecular sieve for 40-45 minutes.
Further, the low-odor antibacterial polyethylene material is prepared from the following raw materials in parts by weight: 80-90 parts of high-density polyethylene, 0.6-1 part of self-made silver-carrying molecular sieve, 10-18 parts of talcum powder, 0.2-0.5 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
Further, the high-density polyethylene is obtained by blending HDPE5000S material and HDPE5703 material.
Further, the compound antioxidant is obtained by compounding antioxidant 168 and 1010 according to a ratio of 1: 1.
Further, the preparation method of the low-odor antibacterial polyethylene material comprises the following steps: mixing high-density polyethylene, a self-made silver-carrying molecular sieve, talcum powder, a compound antioxidant and vinyl bis stearamide, and then extruding the mixture by using a double-screw extruder, wherein the temperature of the extruder is controlled to be 130-plus 180 ℃, the vacuum is (-0.7) MPa- (-0.8) MPa, the rotating speed of a main machine is 400-plus 500r/min, and the feeding rotating speed is controlled to be 300-plus 400 r/min; and cooling, drawing, dehydrating and granulating by a granulator to obtain the low-odor antibacterial polyethylene material.
In conclusion, the beneficial effects of the invention are as follows: the invention carries out mesoporous treatment on the microporous ZSM-5 molecular sieve at normal temperature and normal pressure, greatly improves the ion exchange capacity of the molecular sieve, is suitable for the pore passage for silver ions to enter more than 96 percent, uses tetrapropylammonium hydroxide solution to soak the ZSM-5 treated by sodium hydroxide to replace the sodium ions in the mesopores of the molecular sieve, is beneficial to the silver ions to enter the mesopores for fixation, has the silver carrying capacity of up to 43.36WT percent, improves the silver carrying capacity by about 2 percent compared with the silver carrying capacity of the commonly used silver carrying NaY type zeolite molecular sieve, obviously improves the antibacterial effect, greatly exerts the antibacterial effect of Ag after being added into a high molecular modification material, changes the mesopore structure and the outer shrinkage cavity of the silver carrying ZSM-5, fixes the silver in the mesopores, does not remove the silver in a stable state, and has a long-term existence of the silver because the micropore structure is not isolated, solves the problems of durability caused by silver migration and odor of high molecular materials in the silver-based antibacterial materials.
The microporous ZSM-5 molecular sieve is subjected to mesoporous treatment by adopting sodium hydroxide and tetrapropylammonium hydroxide at normal temperature and normal pressure, so that silicon and aluminum in the ZSM-5 molecular sieve are removed, a framework of the molecular sieve is reserved, the pore diameter is 5-50nm after mesopores are formed, the structure of the molecular sieve is suitable for entering organic micromolecules and Ag +, the ion exchange capacity of the molecular sieve is greatly improved, and the pore passage suitable for entering silver ions is up to more than 96%. Ammonium ions in the molecular sieve framework after the ammonification treatment are beneficial to the fixation of the elemental silver in the molecular sieve mesopores, and the silver and organic micromolecules are absorbed and brought into the inner walls of the ZSM-5 pore channels by utilizing the effective structural shape and size of ZSM-5 pore openings and the bending characteristic of the pore channels and showing the great selectivity characteristics to the sizes and shapes of reactants and product molecules of resin materials, so that the silver and organic micromolecules are kept in the permanent antibacterial capacity of the silver. The modified material can be used as a raw material of a low-odor antibacterial polyethylene material, so that the bacteriostatic ability of the material can be maintained, and small molecular products such as toluene, formaldehyde and the like which are residual in a high molecular modified material can enter a cavity and a pore passage, namely be adsorbed by ZSM-5, so that the emission of VOC gas in the use process of automobiles and household appliances is greatly reduced, the odor performance is greatly reduced, and the use environment and the odor are effectively improved. In the silver-carrying process, because the ZSM-5 molecular sieve contains cations such as alkali metal sodium ions, organic amine ions and the like, the silver ions can be promoted to be generated only by soaking in a silver nitrate solution, the operation at high temperature and high pressure is not required, the operation method is simple and convenient, and the industrial production can be carried out. The ZSM-5 molecular sieve is dried in a microwave drying oven at a temperature of 40 ℃. The calcination process is divided into two sections, wherein the first section is arranged at 200 ℃, which is beneficial to the attachment and shaping of silver in the pore canal and avoids the loss of silver caused by the rapid flow of water vapor in a high-temperature state, the second section is arranged at 320-.
Drawings
FIG. 1 and FIG. 2 are surface electron micrographs of the ZSM-5 molecular sieve after the mesoporous treatment.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
1. A method for mesoporous processing of a ZSM-5 molecular sieve at normal temperature and normal pressure comprises the following specific steps:
2kg of microporous ZSM-5 molecular sieve is uniformly stirred in 6L of 3mol/L sodium hydroxide solution and then soaked for 2 hours, the solution is filtered, pumped and washed to obtain a filter cake 1, the filter cake 1 is placed in 5L of 1mol/L tetrapropylammonium hydroxide solution and then stirred and then soaked for 2 hours, and the filter cake 2 is filtered, pumped and dried to obtain a wet ZSM-5 molecular sieve with the average particle size of 7 microns and the average pore size of 30 nm.
2. The method for preparing the self-made silver-carrying molecular sieve by using the ZSM-5 molecular sieve as the carrier comprises the following specific steps:
and (3) putting the obtained wet ZSM-5 molecular sieve filter cake into 5L of 4mol/L silver nitrate solution, soaking for 2 hours, taking out, draining, drying in a microwave drying oven at the temperature of 40 ℃ for 35 minutes to obtain an unshaped self-made silver-carrying molecular sieve, calcining, shaping, taking out, cooling, sealing and packaging, and marking as the ZSM-5 self-made silver-carrying molecular sieve.
Further, the calcination and sizing are to place the unshaped self-made silver-carrying molecular sieve in a muffle furnace, dry the unshaped self-made silver-carrying molecular sieve at 200 ℃ for 30 minutes, gradually heat the unshaped self-made silver-carrying molecular sieve to 320 ℃ and calcine the unshaped self-made silver-carrying molecular sieve for 45 minutes to obtain the unshaped self-made silver-carrying molecular sieve.
Example 2
1. A method for mesoporous processing of a ZSM-5 molecular sieve at normal temperature and normal pressure comprises the following specific steps:
uniformly stirring 2kg of microporous ZSM-5 molecular sieve in 7L of 2mol/L sodium hydroxide solution, soaking for 2 hours, filtering, pumping, washing to obtain a filter cake 1, putting the filter cake 1 into 4L of 1.5mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, pumping to obtain a filter cake 2, and obtaining the wet ZSM-5 molecular sieve with the average particle size of 10 mu m and the average pore size of 16 nm.
2. The method for preparing the self-made silver-carrying molecular sieve by using the ZSM-5 molecular sieve as the carrier comprises the following specific steps:
and (3) putting the obtained wet ZSM-5 molecular sieve filter cake into 5L of 4mol/L silver nitrate solution, soaking for 2 hours, taking out, draining, drying in a microwave drying oven at the temperature of 40 ℃ for 35 minutes to obtain an unshaped self-made silver-carrying molecular sieve, calcining, shaping, taking out, cooling, sealing and packaging, and marking as the ZSM-5 self-made silver-carrying molecular sieve.
Further, the calcination and sizing are to place the unshaped self-made silver-carrying molecular sieve in a muffle furnace, dry the unshaped self-made silver-carrying molecular sieve at 200 ℃ for 35 minutes, gradually heat the unshaped self-made silver-carrying molecular sieve to 330 ℃ and calcine the unshaped self-made silver-carrying molecular sieve for 40 minutes to obtain the unshaped self-made silver-carrying molecular sieve.
Example 3
A method for mesoporous processing of a ZSM-5 molecular sieve at normal temperature and normal pressure comprises the following specific steps:
uniformly stirring 2kg of microporous ZSM-5 molecular sieve in 8L of 2mol/L sodium hydroxide solution, soaking for 2 hours, filtering, pumping, washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 1mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, pumping to obtain a filter cake 2, and obtaining the wet ZSM-5 molecular sieve with the average particle size of 11 microns and the average pore size of 20 nm.
2. The method for preparing the self-made silver-carrying molecular sieve by using the ZSM-5 molecular sieve as the carrier comprises the following specific steps:
and (3) soaking the obtained wet ZSM-5 molecular sieve filter cake in 6L of 3.5mol/L silver nitrate solution for 2 hours, taking out, draining, drying in a microwave drying oven at the temperature of 40 ℃ for 30 minutes to obtain an unshaped self-made silver-carrying molecular sieve, calcining, shaping, taking out, cooling, sealing and packaging to identify the ZSM-5 self-made silver-carrying molecular sieve.
Further, the calcination and sizing are to place the unshaped self-made silver-carrying molecular sieve in a muffle furnace, dry the unshaped self-made silver-carrying molecular sieve at 200 ℃ for 30 minutes, gradually heat the unshaped self-made silver-carrying molecular sieve to 330 ℃ and calcine the unshaped self-made silver-carrying molecular sieve for 45 minutes to obtain the unshaped self-made silver-carrying molecular sieve.
Example 4
A method for mesoporous processing of a ZSM-5 molecular sieve at normal temperature and normal pressure comprises the following specific steps:
uniformly stirring 2kg of microporous ZSM-5 molecular sieve in 6L of 3.5mol/L sodium hydroxide solution, soaking for 2 hours, filtering, draining and washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 1.5mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, draining to obtain a filter cake 2, and obtaining the ZSM-5 molecular sieve with the average particle size of 6 microns and the average pore size of 31 nm.
2. The method for preparing the self-made silver-carrying molecular sieve by using the ZSM-5 molecular sieve as the carrier comprises the following specific steps:
and (3) putting the obtained wet ZSM-5 molecular sieve filter cake into 5L of 4mol/L silver nitrate solution, soaking for 2 hours, taking out, draining, drying in a microwave drying oven at the temperature of 40 ℃ for 30 minutes to obtain an unshaped self-made silver-carrying molecular sieve, calcining, shaping, taking out, cooling, sealing and packaging, and marking as the ZSM-5 self-made silver-carrying molecular sieve.
Further, the calcination and sizing are to place the unshaped self-made silver-carrying molecular sieve in a muffle furnace, dry the unshaped self-made silver-carrying molecular sieve at 200 ℃ for 35 minutes, gradually heat the unshaped self-made silver-carrying molecular sieve to 325 ℃, and calcine the unshaped self-made silver-carrying molecular sieve for 45 minutes to obtain the unshaped self-made silver-carrying molecular sieve.
Example 5
The silver-loaded ZSM-5 molecular sieve prepared in example 1 is used for preparing the low-odor antibacterial polyethylene material, and the specific steps are as follows:
the low-odor antibacterial polyethylene material comprises the following raw materials in parts by weight: 72 parts of HDPE5000S material, 18 parts of HDPE5703 material, 0.6 part of self-made silver-carrying molecular sieve, 10 parts of talcum powder, 0.2 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
Further, the compound antioxidant is obtained by compounding antioxidant 168 and 1010 according to a ratio of 1: 1.
Further, the preparation method of the low-odor antibacterial polyethylene material comprises the following steps: mixing HDPE5000S material, HDPE5703 material, self-made silver-carrying molecular sieve, talcum powder, compound antioxidant and vinyl bis stearamide, and extruding by a double-screw extruder, wherein the temperature of the extruder is controlled to be 130-180 ℃, and the temperature from feeding to a machine head is 130 ℃ in a first area, 150 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and 170 ℃ in a fifth area. The vacuum is (-0.7) MPa, the rotating speed of the main machine is 400r/min, and the feeding rotating speed is controlled at 300 r/min; and cooling, drawing, dehydrating and granulating by a granulator to obtain the low-odor antibacterial polyethylene material.
Example 6
The silver-loaded ZSM-5 molecular sieve prepared in example 2 is adopted to prepare the low-odor antibacterial polyethylene material, and the specific steps are as follows:
the low-odor antibacterial polyethylene material comprises the following raw materials in parts by weight: 69 parts of HDPE5000S material, 17 parts of HDPE5703 material, 0.8 part of self-made silver-carrying molecular sieve, 13 parts of talcum powder, 0.4 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
Further, the compound antioxidant is obtained by compounding antioxidant 168 and 1010 according to a ratio of 1: 1.
Further, the preparation method of the low-odor antibacterial polyethylene material comprises the following steps: mixing high-density polyethylene, a self-made silver-carrying molecular sieve, talcum powder, a compound antioxidant and vinyl bis stearamide, and then extruding the mixture by using a double-screw extruder, wherein the temperature of the extruder is controlled between 130 and 180 ℃, and the temperature from feeding to a machine head is 130 ℃ in a first area, 150 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and 170 ℃ in a fifth area. The vacuum is (-0.8) MPa, the rotating speed of the main machine is 500r/min, and the feeding rotating speed is controlled to be 400 r/min; and cooling, drawing, dehydrating and granulating by a granulator to obtain the low-odor antibacterial polyethylene material.
Example 7
The silver-loaded ZSM-5 molecular sieve prepared in example 3 is adopted to prepare the low-odor antibacterial polyethylene material, and the specific steps are as follows:
the low-odor antibacterial polyethylene material comprises the following raw materials in parts by weight: 67 parts of HDPE5000S material, 16 parts of HDPE5703 material, 1.0 part of self-made silver-carrying molecular sieve, 15 parts of talcum powder, 0.3 part of compound antioxidant and 0.3 part of vinyl bis-stearamide.
Further, the compound antioxidant is obtained by compounding antioxidant 168 and 1010 according to a ratio of 1: 1.
Further, the preparation method of the low-odor antibacterial polyethylene material comprises the following steps: mixing high-density polyethylene, a self-made silver-carrying molecular sieve, talcum powder, a compound antioxidant and vinyl bis stearamide, and then extruding the mixture by using a double-screw extruder, wherein the temperature of the extruder is controlled between 130 and 180 ℃, and the temperature from feeding to a machine head is 130 ℃ in a first area, 150 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and 170 ℃ in a fifth area. The vacuum is (-0.7) MPa, the rotating speed of the main machine is 450r/min, and the feeding rotating speed is controlled to be 350 r/min; and cooling, drawing, dehydrating and granulating by a granulator to obtain the low-odor antibacterial polyethylene material.
Example 8
The silver-loaded ZSM-5 molecular sieve prepared in example 4 is adopted to prepare the low-odor antibacterial polyethylene material, and the specific steps are as follows:
the low-odor antibacterial polyethylene material comprises the following raw materials in parts by weight: 64 parts of HDPE5000S material, 16 parts of HDPE5703 material, 1.0 part of self-made silver-carrying molecular sieve, 18 parts of talcum powder, 0.2 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
Further, the compound antioxidant is obtained by compounding antioxidant 168 and 1010 according to a ratio of 1: 1.
Further, the preparation method of the low-odor antibacterial polyethylene material comprises the following steps: mixing high-density polyethylene, a self-made silver-carrying molecular sieve, talcum powder, a compound antioxidant and vinyl bis stearamide, and then extruding the mixture by using a double-screw extruder, wherein the temperature of the extruder is controlled between 130 and 180 ℃, and the temperature from feeding to a machine head is 130 ℃ in a first area, 150 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and 170 ℃ in a fifth area. The vacuum is (-0.7) MPa, the rotating speed of the main machine is 500r/min, and the feeding rotating speed is controlled at 300 r/min; and cooling, drawing, dehydrating and granulating by a granulator to obtain the low-odor antibacterial polyethylene material.
Structural performance test of ZSM-5 molecular sieve
1.1 preparation of Experimental materials
Sample 1: uniformly stirring the microporous ZSM-5 molecular sieve in 6L of 4.5mol/L sodium hydroxide solution, soaking for 2 hours, filtering, pumping, washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 1mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, pumping to obtain a filter cake 2, and obtaining the wet ZSM-5 molecular sieve; and then soaking the silver-loaded molecular sieve in 5L of 4mol/L silver nitrate solution for 2 hours, taking out, filtering, drying, placing in a microwave drying oven at the temperature of 40 ℃ for drying for 35 minutes to obtain an unshaped homemade silver-loaded molecular sieve, placing the unshaped homemade silver-loaded molecular sieve in a muffle furnace, drying at the temperature of 200 ℃ for 30 minutes, gradually heating to 320 ℃, calcining for 45 minutes, taking out, cooling, sealing and packaging to identify the ZSM-5 homemade silver-loaded molecular sieve.
Sample 2: uniformly stirring the microporous ZSM-5 molecular sieve in 6L of 0.5mol/L sodium hydroxide solution, soaking for 2 hours, filtering, draining and washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 1mol/L tetrapropyl ammonium hydroxide solution, stirring, soaking for 2 hours, filtering, draining to obtain a filter cake 2, and obtaining the ZSM-5 molecular sieve; and then soaking the silver-loaded molecular sieve in 5L of 4mol/L silver nitrate solution for 2 hours, taking out, filtering, drying, placing in a microwave drying oven at the temperature of 40 ℃ for drying for 35 minutes to obtain an unshaped homemade silver-loaded molecular sieve, placing the unshaped homemade silver-loaded molecular sieve in a muffle furnace, drying at the temperature of 200 ℃ for 30 minutes, gradually heating to 320 ℃, calcining for 45 minutes, taking out, cooling, sealing and packaging to identify the ZSM-5 homemade silver-loaded molecular sieve.
Sample 3: uniformly stirring the microporous ZSM-5 molecular sieve in 6L of 2mol/L sodium hydroxide solution, soaking for 2 hours, filtering, draining and washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 3mol/L tetrapropyl ammonium hydroxide solution, stirring, soaking for 2 hours, filtering, draining to obtain a filter cake 2, and obtaining the ZSM-5 molecular sieve; and then soaking the silver-loaded molecular sieve in 5L of 4mol/L silver nitrate solution for 2 hours, taking out, filtering, drying, placing in a microwave drying oven at the temperature of 40 ℃ for drying for 35 minutes to obtain an unshaped homemade silver-loaded molecular sieve, placing the unshaped homemade silver-loaded molecular sieve in a muffle furnace, drying at the temperature of 200 ℃ for 30 minutes, gradually heating to 320 ℃, calcining for 45 minutes, taking out, cooling, sealing and packaging to identify the ZSM-5 homemade silver-loaded molecular sieve.
Sample 4: uniformly stirring the microporous ZSM-5 molecular sieve in 6L of 2mol/L sodium hydroxide solution, soaking for 2 hours, filtering, draining and washing to obtain a filter cake 1, putting the filter cake 1 into 5L of 0.5mol/L tetrapropyl ammonium hydroxide solution, stirring, soaking for 2 hours, filtering, draining to obtain a filter cake 2, and obtaining the ZSM-5 molecular sieve; and then soaking the silver-loaded molecular sieve in 5L of 4mol/L silver nitrate solution for 2 hours, taking out, filtering, drying in a microwave drying oven at the temperature of 40 ℃ for 35 minutes to obtain an unshaped homemade silver-loaded molecular sieve, then placing the unshaped homemade silver-loaded molecular sieve in a muffle furnace, drying at the temperature of 200 ℃ for 30 minutes, gradually heating to 320 ℃, calcining for 45 minutes, taking out, cooling, sealing and packaging to identify the ZSM-5 homemade silver-loaded molecular sieve.
1.2 Experimental methods
The specific surface area and pore structure were determined by a specific surface area and pore size analyzer, and the pore structure parameters of BET specific surface area and mesoporous pore volume were determined for the molecular sieves prepared in samples 1-2 and examples 1-4, and compared with untreated ZSM-5 molecular sieves, with four decimal places being retained as shown in table 1.
The silver loading test was performed on the molecular sieves prepared in samples 3 to 4 and examples 1 to 4, and the results are shown in table 2.
The silver carrying capacity calculation method comprises the following steps:
WT％＝[(L1×M1)-(L2×M2)]×107.9×98.8/G
wherein the molar concentration of the silver nitrate initial liquid is M1(ii) a The molar concentration of the collected liquid after soaking and washing with silver nitrate is M2(ii) a The volume of the silver nitrate initial liquid is L1(ii) a The volume of the collecting solution after soaking and washing with silver nitrate is L2(ii) a The molar mass of silver is 107.9; the dried silver-loaded ZSM-5 molecular sieve has the mass G; the recovery rate of the ZSM-5 molecular sieve filter cake is 98.8 percent; the weight percentages are expressed by WT%.
1.3 results of the experiment
TABLE 1
According to experimental results, the specific surface area and the mesoporous pore volume of the ZSM-5 molecular sieve treated by the sodium hydroxide solution are increased compared with those of an untreated molecular sieve, but the concentration of the sodium hydroxide solution has a great influence on the specific surface area and the mesoporous pore volume of the ZSM-5 molecular sieve. When the concentration of the sodium hydroxide solution is high, the reaction quantity of aluminum elements and the like in the molecular sieve is large, the specific surface area is larger than that of an untreated molecular sieve, the particle size is reduced after treatment, and meanwhile, the pore diameter is increased. The sodium hydroxide also affects the silver loading, and the high sodium hydroxide concentration expands pores, but the silver loading of sample 1 is large, but the silver loading effect is unstable due to high permeability and high viscosity.
TABLE 2
| Item | Mesopore diameter distribution/(um) | Average pore diameter (um) | Silver loading/(WT%) |
| Untreated molecular sieves | 0.5-3 | 2 | 2.05 |
| Example 1 | 12-48 | 30 | 43.18 |
| Example 2 | 7-25 | 16 | 27.9 |
| Example 3 | 10-30 | 20 | 30.4 |
| Example 4 | 13-50 | 31 | 43.36 |
| Sample 3 | 11-32 | 22 | 26.83 |
| Sample No. 4 | 6-22 | 14 | 18.07 |
Second, the antibacterial performance test of the low-odor antibacterial polyethylene material
2.1 materials of the experiment
Sample 5: the low-odor antibacterial polyethylene material comprises the following components in parts by weight: 71 parts of HDPE5000S material, 18 parts of HDPE5703 material, 0.2 part of self-made silver-carrying molecular sieve, 10 parts of talcum powder, 0.2 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
Sample 6: the low-odor antibacterial polyethylene material comprises the following components in parts by weight: 71 parts of HDPE5000S material, 18 parts of HDPE5703 material, 0 part of self-made silver-carrying molecular sieve, 10 parts of talcum powder, 0.2 part of compound antioxidant and 0.3 part of vinyl bis-stearamide.
The preparation method of the self-made silver-loaded molecular sieve and the low-odor antibacterial polyethylene material is the same as that of the example 1.
2.2 Experimental methods
The low-odor antimicrobial primary polymer materials prepared in examples 5-8 and samples 5-6 were tested for their antimicrobial properties by the method described in GB/T31402-2015 test method for antimicrobial properties on plastic surfaces, and the antimicrobial rates were calculated and the results are shown in Table 3.
Wherein the antibacterial rate is (Ct-Tt)/Ct, Ct is the average value of viable count of a 24h control sample (CFU/cm2), Tt is the average value of viable count of a 24h sample (CFU/cm2), and the test strains are escherichia coli and staphylococcus aureus.
2.3 results of the experiment
TABLE 3
Third, mechanical property and adsorptivity test of low-odor antibacterial polyethylene material
3.1 Experimental materials
Examples 5-8 and samples 5-6.
3.2 Experimental methods
And (3) testing mechanical properties: testing the tensile strength of a sample according to GB/T1040.5-2006 in MP under the environment with the temperature of 23 ℃ and the humidity of 50%; the elongation at break of the test specimen at a test speed of 5mm/min, expressed in percent (%) as in GB/T1040.3-2006; testing the flexural modulus of the sample according to GB/T9341-; testing the notched Izod impact strength of the sample according to GB/T1843-2008, unit kJ/m 2; the melt index of the sample was measured in GB/T3682-2008 in g/10 min.
Adsorption test: the odor grade is detected according to an odor test method of the non-metallic material in the automobile of Changan automobile GmbH, Chongqing, namely 'odor test Specification of the non-metallic material in the automobile'. VS-00.28-L-06021, and the odor grade is less than or equal to 2, which indicates that the odor irritation is quite small, the smell is hardly felt and the harm to the human body is extremely small.
The mechanical properties test results and the adsorption test results are shown in table 4.
3.3 results of the experiment
TABLE 4
According to experimental results, the self-made silver-loaded molecular sieve prepared by using the ZSM-5 molecular sieve subjected to mesoporous treatment as the carrier has excellent adsorption capacity when being used as a preparation raw material of a low-odor antibacterial polyethylene material, so that the VOC gas emission in the use process of automobiles and household appliances is greatly reduced, the odor is greatly reduced, and the use environment and the odor are effectively improved.
Claims (9)
1. A mesoporous treatment method of a ZSM-5 molecular sieve is characterized in that the mesoporous ZSM-5 molecular sieve is obtained by carrying out ammonification treatment on a microporous ZSM-5 molecular sieve under the conditions of normal temperature and normal pressure.
2. The method for mesoporous treatment of ZSM-5 molecular sieve as claimed in claim 1, wherein the ammonification treatment comprises the following steps: uniformly stirring the microporous ZSM-5 molecular sieve in 2-3.5mol/L sodium hydroxide solution, soaking for 2 hours, filtering, pumping, washing to obtain a filter cake 1, putting the filter cake 1 into 1-1.5mol/L tetrapropylammonium hydroxide solution, stirring, soaking for 2 hours, filtering, pumping to obtain a filter cake 2, and obtaining the wet ZSM-5 molecular sieve.
3. The method for mesoporous treatment of the ZSM-5 molecular sieve of claim 1 or 2, wherein the ZSM-5 molecular sieve obtained by mesoporous treatment has a particle size of 5-10 μm and a pore size of 5-50 nm.
4. The application of the ZSM-5 molecular sieve is characterized in that the ZSM-5 molecular sieve is used as a carrier of a self-made silver-loaded molecular sieve, and the self-made silver-loaded molecular sieve is used as one of raw materials for preparing a low-odor antibacterial polyethylene material.
5. The use of the ZSM-5 molecular sieve of claim 4, wherein the self-made silver-loaded molecular sieve is prepared by the method comprising: soaking the ZSM-5 molecular sieve in 4mol/L silver nitrate solution for 2h, drying by filtering, drying by adopting microwave for 30-35min to obtain an unshaped self-made silver-carrying molecular sieve, and then calcining and shaping to obtain the self-made silver-carrying molecular sieve.
6. The application of the ZSM-5 molecular sieve of claim 5, wherein the calcination and the sizing are carried out by placing the unshaped homemade silver-carrying molecular sieve in a muffle furnace, drying at 200 ℃ for 30-35min, and then heating to 320-330 ℃ for calcination for 40-45 min.
7. The application of the ZSM-5 molecular sieve of claim 4, wherein the low-odor antibacterial polyethylene material comprises, by weight, 80-90 parts of high-density polyethylene, 0.6-1 part of self-made silver-carrying molecular sieve, 10-18 parts of talcum powder, 0.2-0.5 part of compound antioxidant and 0.3 part of vinyl bis stearamide.
8. The use of the ZSM-5 molecular sieve as claimed in claim 7, wherein the low-odor antibacterial polyethylene material is prepared by: mixing high-density polyethylene, a self-made silver-carrying molecular sieve, talcum powder, a compound antioxidant and vinyl bis-stearamide, then extruding the mixture by using a double-screw extruder, and cooling, drawing, dehydrating and granulating the mixture by using a granulator to obtain the low-odor antibacterial polyethylene material.
9. The use of a ZSM-5 molecular sieve as claimed in claim 8, wherein the extrusion conditions are: the temperature of the extruder is controlled between 130 ℃ and 180 ℃, the vacuum is (-0.7) MPa- (-0.8) MPa, the rotating speed of the main machine is controlled at 400 ℃ and 500r/min, and the feeding rotating speed is controlled at 300 ℃ and 400 r/min.
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