WO2019178925A1 - Preparation method for novel purification material with catalytic oxidation of formaldehyde and sterilization functions - Google Patents

Preparation method for novel purification material with catalytic oxidation of formaldehyde and sterilization functions Download PDF

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WO2019178925A1
WO2019178925A1 PCT/CN2018/086776 CN2018086776W WO2019178925A1 WO 2019178925 A1 WO2019178925 A1 WO 2019178925A1 CN 2018086776 W CN2018086776 W CN 2018086776W WO 2019178925 A1 WO2019178925 A1 WO 2019178925A1
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formaldehyde
catalytic oxidation
fiber
oxide
active component
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PCT/CN2018/086776
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French (fr)
Chinese (zh)
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熊菊霞
严方升
李普煊
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深圳市普瑞美泰环保科技有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1026—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/104—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/106—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20792—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/91—Bacteria; Microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air

Definitions

  • the present application relates to the field of air purification, and more particularly to a method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilization function.
  • Formaldehyde (HCHO) is one of the most important pollutants.
  • the source of formaldehyde in the environment is extremely extensive. It is usually produced by natural and artificial methods.
  • the formaldehyde in indoor air mainly comes from interior decoration, laminate flooring, furniture, paints and so on. Will emit formaldehyde gas. As time goes by, it will gradually release to the surrounding environment. Long-term exposure to low concentrations of formaldehyde may cause headache, insomnia, finger tremor, vision loss and other symptoms. High concentration of formaldehyde may cause leukemia to the eyes, respiratory tract and skin. , nasopharyngeal cancer and other diseases.
  • the World Health Organization stipulates that the indoor formaldehyde concentration threshold is 0.08 mg/m 3 . When the concentration exceeds the standard, purification treatment measures are required.
  • the concentration of formaldehyde in indoor air is related to the following four factors: indoor air circulation, indoor material usage, indoor relative humidity, and indoor temperature. It will increase formaldehyde volatilization under high temperature, high humidity and negative pressure. According to statistics, within six months after the interior decoration, the living room of formaldehyde exceeds 80%, the conference hall and office space are close to 100%; while in three years, it still reaches more than 50%, and the release time of formaldehyde in the partition is as long as 3-15 years. How to remove formaldehyde quickly and effectively is a hot spot in technology research and also a market demand.
  • An important and commonly used method is to purify formaldehyde with an air purifier.
  • the formaldehyde filter used in the air purifier is to load the catalytic material on the surface of the porous carrier particle material, and then the particulate material.
  • the porous carrier material used in order to ensure that the wind resistance is small and does not fall off, the porous carrier material used must be relatively large particles, so that the purification effect will be affected; also the material is combined with the HEPA material, so that Although solving some problems, the filter is wasteful of precious metal resources due to the one-time HEPA material, and the use cost is high; at the same time, such materials can only be sterilized by purifying formaldehyde, and another layer of sterilizing material is needed when sterilizing is required, so that The resistance of the filter increases.
  • the purpose of the present application is to overcome the deficiencies of the prior art and to provide a method for preparing a new purification material having catalytic oxidation of formaldehyde and a bactericidal function.
  • a porous adsorbent material such as zeolite, silica gel, alumina, activated carbon or polydivinylbenzene as a carrier, a noble metal material and a rare earth metal material having catalytic function of oxidizing formaldehyde, and a substance containing silver, zinc or copper having a bactericidal function Loaded on the carrier material in a certain proportion, and then the carrier material loaded with the active ingredient is combined with polyester, polyethylene, polypropylene or nylon material to form a fiber, and then the fiber is processed into a non-woven fabric, thereby preparing
  • the invention discloses a purification material which simultaneously catalyzes the oxidation of formaldehyde and a sterilizing function.
  • the material catalyzes the high dispersion degree of the oxidizing component and the bactericidal active component, and has a large contact area with formaldehyde and a pathogen, and can completely catalyze oxidative decomposition, fast and efficient killing while adsorbing formaldehyde.
  • the sterilizing bacteria show excellent formaldehyde removal and bactericidal properties.
  • the method of the invention has low precious metal content, reasonable cost, small wind resistance, long-term use, good stability, and no additional energy device such as light, electricity and heat, and is suitable for air purification, especially suitable for air purifier filter and mask. Such products provide people with a clean and safe living environment and have broad application prospects.
  • a preparation method for purifying a new material which catalyzes the oxidation of formaldehyde and a bactericidal function comprising the following steps:
  • Step one using a porous adsorbent material as a carrier;
  • Step 2 supporting a noble metal having a function of catalytic oxidation of formaldehyde, a rare earth metal material, a substance containing silver, zinc or copper having a bactericidal active component on the carrier material;
  • Step 3 combining the carrier material loaded with the active functional component with the polymer material to form a fiber
  • the fiber is processed into a non-woven fabric to complete the preparation of the purified material.
  • the porous adsorbent material is one or more of zeolite, silica gel, alumina, activated carbon and polydivinylbenzene; the total amount of the porous adsorbent material is the purification material. 0.1% to 30% of the quality of the finished product; the noble metal includes one or more of platinum, palladium, rhodium, iridium, gold and rare earth metal ruthenium, and the total amount thereof is the finished product of the purification material according to the elemental mass thereof. 0.001% to 10% of the mass.
  • the porous adsorbent material is zeolite and alumina; the total amount of the porous material is preferably 0.5% to 10%; the total amount of the precious metal is the best quality of the finished product of the purified material. 0.05% to 1%.
  • the noble metal active component is derived from any one of a noble metal element, a noble metal oxide, a noble metal complex or a noble metal inorganic salt or a mixture of at least two;
  • the rare earth metal cerium is derived from cerium oxide And one or a mixture of at least two of cerium chloride, cerium sulfate, cerium nitrate, ammonium cerium nitrate.
  • the oxide is platinum oxide, palladium oxide, cerium oxide, cerium oxide, gold oxide or cerium oxide
  • the noble metal inorganic salt is platinum chloride, palladium chloride, palladium chloride or cerium chloride. , gold chloride or barium chloride or barium sulfate or barium nitrate or ammonium cerium nitrate
  • the noble metal complex is potassium chloroplatinate, chloroplatinic acid or potassium chloroplatinate.
  • the bactericidal active component is one or more of silver, zinc or copper materials, and the total amount is 0.01% to 20% of the mass of the purified material according to the element mass.
  • the bactericidal active component is used in an amount of 0.05% to 5% by mass of the element of the purified material.
  • the copper in the bactericidal active component is derived from copper nitrate or copper chloride or copper sulfate or copper oxide; silver is derived from silver nitrate or silver oxide; zinc is derived from zinc nitrate or zinc chloride or oxidized Zinc; the polymer material includes one or more of polyester, polyethylene, polypropylene and nylon.
  • the third step further comprises the following: the formaldehyde catalytic oxidation active component and the bactericidal active component are first uniformly mixed, and then supported on the carrier material, and then combined with the polymer material. Fibres.
  • the third step further comprises the following: compounding the catalytic oxidation active component and the bactericidal active component with the carrier material respectively, and then mixing the two composite carrier materials.
  • the further technical solution is that the carrier material loaded with the formaldehyde catalytic oxidation and the sterilizing material is added during the melting process of the polymer material, or is compounded on the fiber surface during the spinning process, or is compounded on the fiber surface after the fiber melt-blown is completed. .
  • the further technical scheme is: the fiber loaded with the catalytic oxidation of formaldehyde and the sterilizing active component is processed into a non-woven material by a needle punching or hydroentangling, hot pressing treatment, etc., thereby preparing a new purification product with catalytic oxidation of formaldehyde and sterilization function. material.
  • the carrier particles loaded with formaldehyde catalytic oxidation active components are closely arranged on the surface of the fiber, the carrier particles are uniformly distributed and the coverage is extremely high, and the carrier particles are well fixed on the surface of the fiber material, and are not easy to fall off.
  • the formaldehyde removal rate is close to 100% at room temperature, which can completely oxidize formaldehyde to non-toxic and harmless carbon dioxide and water, and has high sterilization efficiency.
  • the bacteria have no resistance to the composite fiber, the antibacterial effect is as high as 99%, and the cost is low;
  • the preparation process is simple and the preparation conditions are mild: the preparation process of the catalyst is not high on the equipment, and the procedure is relatively simple;
  • low cost low precious metal catalyst content, high formaldehyde removal efficiency, and long-term use, can effectively reduce the cost of precious metals.
  • the combination of the carrier material and the fiber can effectively increase the adsorption capacity of the organic matter, and provides favorable conditions for the adsorption of formaldehyde, thereby facilitating the removal of formaldehyde;
  • 1 is a flow chart of a method for preparing a purified new material having catalytic oxidation of formaldehyde and a bactericidal function.
  • the present application discloses a method for preparing a purified new material having catalytic oxidation of formaldehyde and a bactericidal function, comprising the following steps:
  • Step one using a porous adsorbent material as a carrier;
  • Step 2 supporting a noble metal having a function of catalytic oxidation of formaldehyde, a rare earth metal material, a substance containing silver, zinc or copper having a bactericidal active component on the carrier material;
  • Step 3 combining the carrier material loaded with the active functional component with the polymer material to form a fiber
  • the fiber is processed into a non-woven fabric to complete the preparation of the purified material.
  • the present application adopts one or more of porous adsorbing materials such as zeolite, silica gel, alumina, activated carbon and polydivinylbenzene as a carrier; and arranges precious metals (platinum, palladium, rhodium, iridium, gold) and rare earth metals ( a mixed aqueous solution of one or more compounds in ⁇ ), and then uniformly mixing the carrier and the mixed aqueous solution to prepare a mixture; crystallization treatment of the mixture, after separation, washing, drying, and preparation a modified support material for catalytically oxidizing an active ingredient of formaldehyde; a mixed solution containing one or more of silver, zinc or copper, and then adding the support material to a mixed solution to crystallize the mixture After the crystallization treatment is completed, it is separated, washed, and dried to obtain a modified carrier material having a bactericidal function.
  • porous adsorbing materials such as zeolite, silica gel,
  • the precious metal active component is derived from any one of a noble metal element, a noble metal oxide, a noble metal complex or a noble metal inorganic salt or a mixture of at least two.
  • the rare earth metal active component cerium is derived from one of cerium oxide, cerium chloride, cerium sulfate, cerium nitrate, and cerium ammonium nitrate.
  • the oxide is platinum oxide, palladium oxide, cerium oxide, cerium oxide, gold oxide or cerium oxide
  • the inorganic salt is platinum chloride, palladium chloride, palladium chloride, cerium chloride, gold chloride or chlorinated Barium or barium sulfate or barium nitrate or ammonium cerium nitrate
  • the complex is potassium chloroplatinate, chloroplatinic acid or potassium chloroplatinate (platinum/palladium/iridium/ruthenium/gold).
  • one or more of the supported platinum/palladium/ruthenium/rhenium/gold/ruthenium compounds are 0.005 by mass of the active component. -10%, preferably 0.01% to 1%.
  • copper in the antibacterial active component is derived from copper nitrate/copper chloride/copper sulfate
  • silver is derived from silver nitrate/silver oxide
  • zinc is derived from zinc nitrate/zinc chloride.
  • the total mass percentage of one or more elements of the copper-silver-zinc compound is 0.01% to 10%, preferably 0.05% to 5%.
  • the crystallization temperature is 80-160 ° C
  • the crystallization time is 1-24 h hours.
  • the oven was oven dried at 80 ° C for 2 h.
  • the auxiliary agent in the melting process includes a binder and a dispersion liquid
  • the binder is one of ethylene vinyl acetate copolymer (EVA) or acrylic acid, preferably acrylic acid.
  • the dispersion liquid is one of an antistatic oil, a silver ion resistant electric oil, a phosphate ester, a wax, and a vegetable oil, preferably a phosphate ester.
  • the temperature at which the mixture was injected at the melting temperature was 300 °C.
  • the specific implementation step is to lay the composite fiber on the rotating mesh curtain to form a mixed fiber web of 1-100 mm thickness, wherein the mesh curtain has a mesh number of 50 mesh.
  • the composite fiber is then subjected to needle punching or hydroentangling and hot pressing.
  • the hot pressing time is 1-30 min, and the hot pressing temperature is 90-200 °C.
  • the fiber and 20g of phosphate ester were placed in a spinning machine with a rotation speed of 2500 rpm, and the dispersion treatment was carried out, and then the zeolite particles loaded with the catalytic oxidation and sterilization function of formaldehyde were added to the 0.02% by mass of the platinum element to make the zeolite.
  • the fiber is thoroughly melted and mixed at 290 ° C, and the synthetic fiber is melt-spun and extruded through a spinneret.
  • a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded, cut, and made into a filter for removing formaldehyde sterilization.
  • cerium chloride having a Rh content of 0.1 g, silver nitrate having an elemental Ag content of 0.2 g, zinc nitrate having an elemental Zn content of 0.3 g, and copper nitrate having an elemental Cu content of 0.5 g dissolved in water to form a mixed solution, and then 100 g of the zeolite precursor was uniformly mixed with the mixed aqueous solution to obtain a mixed solution. Further, the mixed solution was crystallized at 100 ° C to prepare zeolite particles loaded with the catalyst.
  • polyester fiber and 20 g of phosphate ester were placed in an opener at a rotation speed of 2,500 rpm, opened and dispersed, and the synthetic fiber was melt-spun and extruded through a spinneret.
  • the zeolite particles loaded with the catalyst and the bactericide were then sprayed onto the surface of the molten fiber at a mass percentage of cerium of 0.02%.
  • a mixed fiber web of 2 mm is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
  • the preparation element has a Pd content of 0.05 g of palladium chloride and a platinum chloride having an elemental Pt content of 0.05, a silver nitrate having an elemental Ag content of 0.2 g, a zinc nitrate having an elemental Zn content of 0.3 g, and an elemental Cu content of 0.5 g.
  • the copper nitrate is dissolved in water to form a mixed solution, and then the modified 100 g of the zeolite precursor is uniformly mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C to prepare a simultaneous catalytic oxidation of formaldehyde.
  • Active component and bactericidal function of zeolite particles then 790g of polyester fiber and 10g of phosphate ester are placed in a 2500 rev / min opener, opened and dispersed, and then loaded with catalyst and fungicide
  • the zeolite particles are added to the catalyst-loaded zeolite particles at a total mass percentage of 0.02% of the platinum and palladium elements, so that the zeolite and the fibers are thoroughly melted and mixed at 300 ° C; and the synthetic fibers are melt-spun and extruded through a spinneret;
  • a 2mm thick mixed fiber web is formed on the 50-mesh rotating screen curtain; the mixed fiber web is subjected to needle punching and hot pressing treatment, wherein the hot pressing time is 30 min, and the hot pressing temperature is 110 ° C.
  • Nonwovens prepared Finally, the non-woven material is folded, cut, removing the filter is made of formaldehyde sterilization.
  • the content of the preparation element Au is 0.1 g of chloroauric acid and the element Ce is 0.3 g of cerium nitrate, the elemental Ag content is 0.2 g of silver nitrate, the elemental Zn content is 0.3 g of zinc nitrate, and the element Cu content is 0.5.
  • the gram of copper nitrate is dissolved in water to form a mixed solution, and then the modified 100 g of the zeolite precursor is mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C to prepare a simultaneous catalytic oxidation.
  • the active component of formaldehyde and the granulating zeolite particles, then 890 g of polyester fiber and 10 g of phosphate are placed in an opener at a speed of 2500 rpm, opened and dispersed, and then loaded with a catalyst and
  • the zeolite particles of the bactericide are added to the catalyst-loaded zeolite particles at a mass percentage of 0.02% of the gold element, the zeolite and the fibers are sufficiently melt-mixed at 320 ° C, and the synthetic fibers are melt-spun and extruded through a spinneret.
  • a mixed web of 2 mm thick was formed on a rotating screen of 50 mesh; the mixed fiber web was subjected to needle punching and hot pressing, wherein the hot pressing time was 30 min, the hot pressing temperature was 120 ° C, and the non-woven fabric was prepared. Cloth material, finally, the non-woven material is folded and sheared to make a filter for removing formaldehyde sterilization. According to the analysis, on the one hand, the formation of highly oxidized metal ions by CeO2 with high specific surface enhances the adsorption capacity of formaldehyde.
  • CeO2 with high specific surface area can provide more oxygen vacancies and form a conjugation effect of Au-Ce, on which oxygen molecules are converted into active species to participate in the reaction, and thus have higher Formaldehyde catalytic activity.
  • the carrier element Rh content is 0.05 g of cerium chloride and the element Pd content is 0.05 g of palladium chloride and 100 g of polydivinylbenzene are mixed to prepare a carrier particle loaded with formaldehyde-catalyzed oxidation; and the elemental Ag content is 0.2.
  • the mixed solution is crystallized at 100 ° C to prepare zeolite particles loaded with the bactericidal active ingredient.
  • 790 g of the polyester fiber and 10 g of the phosphate ester were placed in an opener at a rotation speed of 2,500 rpm, and the dispersion treatment was carried out, and the synthetic fiber was melt-spun and extruded through a spinneret.
  • the polydivinylbenzene particles loaded with the formaldehyde catalytically oxidizing active ingredient are mixed with the zeolite particles loaded with the above bactericidal active ingredient in a ratio of 1:1, and then sprayed on the surface of the fiber at a total mass percentage of 0.01% of palladium and ruthenium; Then, a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
  • the catalyst particles are prepared by mixing platinum chloride with a Pt content of 0.1 g and 100 g of polydivinylbenzene; and silver nitrate having an elemental Ag content of 0.3 g and zinc nitrate having an elemental Zn content of 0.2 g are prepared.
  • the copper nitrate having an elemental Cu content of 0.5 g is dissolved in water to form a mixed solution, and then 100 g of the modified zeolite precursor is uniformly mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C.
  • the zeolite particles loaded with the bactericidal active ingredient Preparing the zeolite particles loaded with the bactericidal active ingredient; then placing 790 g of the polyester fiber and 10 g of the phosphate ester in an opener rotating at 2500 rpm, opening and dispersing, and then passing the synthetic fiber through the spinneret Melt spinning and extrusion. Subsequently, the active ingredient polydivinylbenzene particles loaded with catalytic oxidation of formaldehyde are mixed with the zeolite particles loaded with the above bactericidal active ingredient in a ratio of 1:1, and then the zeolite particles loaded with the catalyst and the bactericide are mass% of the platinum element. 0.01% sprayed on the fiber surface.
  • a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
  • the catalyst particles are prepared by mixing platinum chloride with a Pt content of 0.05 g and ruthenium chloride with an elemental Ru content of 0.05 g and 100 g of alumina molecular sieve; and taking silver nitrate with an elemental Ag content of 0.25 g, The zinc nitrate having an elemental Zn content of 0.3 g and the copper nitrate having an elemental Cu content of 0.3 g are dissolved in water to form a mixed solution, and then 100 g of the modified zeolite precursor is mixed with the mixed aqueous solution to obtain a mixed solution, and then at 100 ° C.
  • the mixed solution is crystallized to prepare zeolite particles loaded with the bactericidal active ingredient; then 790 g of the polyester fiber and 10 g of the phosphate ester are placed in an opener at a rotation speed of 2500 rpm, and the dispersion treatment is carried out. And then, the synthetic fiber is melt-spun and extruded through a spinneret; then, the alumina particles loaded with the formaldehyde-catalyzed active component are mixed with the zeolite particles loaded with the above-mentioned bactericidal active component in a ratio of 1:1, and then platinum is added.
  • the raw material is 100ppm formaldehyde/high purity air mixture (21%O2+79%N2)
  • the reaction gas flow rate is 100ml/min
  • the reaction temperature is 25°C
  • the indoor environmental humidity level RH 80%
  • the gas volumetric space velocity is 80000h-1, and the point at which the reaction is taken for 1h is sampled and analyzed.
  • the formaldehyde removal rate of the formaldehyde-removing catalyst obtained in the present application is more than 99% at room temperature, and the selectivity of carbon dioxide is over 98%; the object of the present application is completed.
  • the present application combines a carrier material loaded with a formaldehyde-catalyzed active ingredient and a bactericidal active ingredient with a polymer material such as polyester, polyethylene, polypropylene, and nylon, and is heated and melted to make the active component and the fiber. Bonding, forming a strong active layer inside and outside the fiber, increasing the specific surface area of the material, facilitating the dispersion of the active component, enabling the formaldehyde to fully contact with the catalyst, and having a good purifying function for formaldehyde; and simultaneously making the germ and the germicidal material Fully contact and quickly kill germs.
  • a polymer material such as polyester, polyethylene, polypropylene, and nylon

Abstract

A preparation method for a novel purification material with catalytic oxidation of formaldehyde and sterilization functions, comprising the following steps: step 1, taking a porous adsorption material as a carrier; step 2, loading precious metal with a catalytic oxidation function of formaldehyde, a rare-earth metal material, a substance containing silver, zinc or copper and having a sterilization active component on the carrier material; step 3, synthetizing the carrier material loaded with the active functional components with a high molecular material to form a fiber; and step 4, processing the fiber into a non-woven fabric to finish the preparation for the purification material.

Description

具有催化氧化甲醛和杀菌功能的净化新材料的制备方法Preparation method of purification new material with catalytic oxidation of formaldehyde and sterilization function
本申请是以申请号为201810246809.0，申请日为2018年3月23日的中国专利申请为基础，并主张其优先权，该申请的全部内容在此作为整体引入本申请中。The present application is based on the Chinese Patent Application No. 2018, 1024, 680, 9.0, filed on Jan. 23, s.
技术领域Technical field
本申请涉及空气净化领域，更具体地说是指具有催化氧化甲醛和杀菌功能的净化新材料的制备方法。The present application relates to the field of air purification, and more particularly to a method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilization function.
背景技术Background technique
据统计，人们生活80％的时间都停留在住宅、办公室和汽车里，因此室内空气质量对人体健康极其重要。甲醛(HCHO)是其中最主要的一种污染物，环境中甲醛来源极其广泛，通常是通过自然和人为的途径产生，室内空气中的甲醛主要来源于室内装饰、复合地板、家具、油漆涂料等都会挥发甲醛气体。随着时间的推移，会逐渐向周围环境释放，长期接触低浓度的甲醛会出现头痛、失眠、手指震颤、视力减退等症状，高浓度的甲醛对眼睛、呼吸道及皮肤的强烈刺激性可引起白血病、鼻咽癌等疾病。世界卫生组织(WHO)规定室内甲醛浓度阈值为0.08mg/m 3，当浓度超标时，需要采取净化处理措施。 According to statistics, people spend 80% of their time in homes, offices and cars, so indoor air quality is extremely important for human health. Formaldehyde (HCHO) is one of the most important pollutants. The source of formaldehyde in the environment is extremely extensive. It is usually produced by natural and artificial methods. The formaldehyde in indoor air mainly comes from interior decoration, laminate flooring, furniture, paints and so on. Will emit formaldehyde gas. As time goes by, it will gradually release to the surrounding environment. Long-term exposure to low concentrations of formaldehyde may cause headache, insomnia, finger tremor, vision loss and other symptoms. High concentration of formaldehyde may cause leukemia to the eyes, respiratory tract and skin. , nasopharyngeal cancer and other diseases. The World Health Organization (WHO) stipulates that the indoor formaldehyde concentration threshold is 0.08 mg/m 3 . When the concentration exceeds the standard, purification treatment measures are required.
室内空气中甲醛浓度的大小与以下四个因素有关：室内空气流通量、室内材料的用量、室内相对湿度、室内温度。在高温、高湿及负压下会加剧甲醛挥发。据统计，室内装修后半年内，甲醛超标起居室达80％，会议厅和办公场所接近100％；而三年内依旧达到50％以上，隔板中的甲醛的释放时间长达3-15年。如何快速有效地去除甲醛是技术研究的热点，也是市场需求。The concentration of formaldehyde in indoor air is related to the following four factors: indoor air circulation, indoor material usage, indoor relative humidity, and indoor temperature. It will increase formaldehyde volatilization under high temperature, high humidity and negative pressure. According to statistics, within six months after the interior decoration, the living room of formaldehyde exceeds 80%, the conference hall and office space are close to 100%; while in three years, it still reaches more than 50%, and the release time of formaldehyde in the partition is as long as 3-15 years. How to remove formaldehyde quickly and effectively is a hot spot in technology research and also a market demand.
目前，甲醛净化处理的方法很多，一种重要且普遍应用的方法是用空气净化器来净化甲醛，空气净化器所用的甲醛过滤网是将催化材料负载在多孔载体颗粒材料表面，再将颗粒材料填入蜂窝状骨架材料中，为了保证风阻小又不会脱落，所使用的多孔载体材料要求必须是比较大的颗粒，这样净化效果就会受到影响；也有将材料与HEPA材料复合在一起，这样虽然解决一些问题，但这种滤网因HEPA材料是一次性的而造成贵金属资源浪费，使用成本高；同时这类材料只净化甲醛不能杀菌，需要杀菌时又得另外复合一层杀菌材料，这样过滤网的阻力增加。At present, there are many methods for formaldehyde purification treatment. An important and commonly used method is to purify formaldehyde with an air purifier. The formaldehyde filter used in the air purifier is to load the catalytic material on the surface of the porous carrier particle material, and then the particulate material. Filled into the honeycomb skeleton material, in order to ensure that the wind resistance is small and does not fall off, the porous carrier material used must be relatively large particles, so that the purification effect will be affected; also the material is combined with the HEPA material, so that Although solving some problems, the filter is wasteful of precious metal resources due to the one-time HEPA material, and the use cost is high; at the same time, such materials can only be sterilized by purifying formaldehyde, and another layer of sterilizing material is needed when sterilizing is required, so that The resistance of the filter increases.
因此需要制造一种同时催化氧化甲醛和杀菌功能的净化新材料，既可以实现双重功能，净化效率高，同时过滤网的阻力小，可长期使用，其技术及经济意义重大，可以满足市场需求。Therefore, it is necessary to manufacture a new purification material which simultaneously catalyzes the oxidation of formaldehyde and the sterilizing function, and can realize dual functions and high purification efficiency. At the same time, the resistance of the filter net is small and can be used for a long time, and its technical and economic significance is significant, which can meet the market demand.
申请内容Application content
本申请的目的在于克服现有技术的缺陷，提供具有催化氧化甲醛和杀菌功能的净化新材料的制备方法。以沸石、硅胶、氧化铝、活性碳、聚二乙烯基苯等多孔吸附材料为载体，将具有催化氧化甲醛功能的贵金属材料和稀土金属材料、及具有杀菌功能的含银、锌或铜的物质按一定比例负载在所述的载体材料上，再将负载有活性成分的载体材料与聚酯、聚乙烯、聚丙烯或尼龙材料复合制成纤维，再将纤维加工成无纺布，从而制成一种同时具备催化氧化甲醛和杀菌功能的净化材料，该材料催化氧化成分及杀菌活性成分的分散度高，与甲醛及病菌接触面积大，能将甲醛吸附的同时彻底催化氧化分解、快速高效杀灭病菌，表现出优异的除甲醛及杀菌性能。本申请方法贵金属含量低，成本合理，风阻小，可长期使用，稳定性好，且无需外加光、电、热等附加能源装置，适 用于空气净化领域，特别适用于空气净化器过滤网及口罩等产品，为人们提供清洁、安全的生活环境，具有较广阔的应用前景。The purpose of the present application is to overcome the deficiencies of the prior art and to provide a method for preparing a new purification material having catalytic oxidation of formaldehyde and a bactericidal function. Using a porous adsorbent material such as zeolite, silica gel, alumina, activated carbon or polydivinylbenzene as a carrier, a noble metal material and a rare earth metal material having catalytic function of oxidizing formaldehyde, and a substance containing silver, zinc or copper having a bactericidal function Loaded on the carrier material in a certain proportion, and then the carrier material loaded with the active ingredient is combined with polyester, polyethylene, polypropylene or nylon material to form a fiber, and then the fiber is processed into a non-woven fabric, thereby preparing The invention discloses a purification material which simultaneously catalyzes the oxidation of formaldehyde and a sterilizing function. The material catalyzes the high dispersion degree of the oxidizing component and the bactericidal active component, and has a large contact area with formaldehyde and a pathogen, and can completely catalyze oxidative decomposition, fast and efficient killing while adsorbing formaldehyde. The sterilizing bacteria show excellent formaldehyde removal and bactericidal properties. The method of the invention has low precious metal content, reasonable cost, small wind resistance, long-term use, good stability, and no additional energy device such as light, electricity and heat, and is suitable for air purification, especially suitable for air purifier filter and mask. Such products provide people with a clean and safe living environment and have broad application prospects.
为实现上述目的，本申请采用以下技术方案：To achieve the above objectives, the present application adopts the following technical solutions:
具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，包括以下步骤：A preparation method for purifying a new material which catalyzes the oxidation of formaldehyde and a bactericidal function, comprising the following steps:
步骤一，以多孔吸附材料为载体；Step one, using a porous adsorbent material as a carrier;
步骤二，将具有催化氧化甲醛功能的贵金属、稀土金属材料、具有杀菌活性组分的含银、锌或铜的物质负载在所述的载体材料；Step 2, supporting a noble metal having a function of catalytic oxidation of formaldehyde, a rare earth metal material, a substance containing silver, zinc or copper having a bactericidal active component on the carrier material;
步骤三，将所述的负载有活性功能组分的载体材料与高分子材料复合制成纤维；Step 3, combining the carrier material loaded with the active functional component with the polymer material to form a fiber;
步骤四，将所述纤维加工成无纺布，完成净化材料的制作。In the fourth step, the fiber is processed into a non-woven fabric to complete the preparation of the purified material.
其进一步技术方案为：所述的多孔吸附材料为沸石、硅胶、氧化铝、活性碳和聚二乙烯基苯中的一种或几种；所述的多孔吸附材料的总用量为所述净化材料成品质量的0.1％～30％；所述的贵金属包括铂、钯、铑、钌、金和稀土金属铈中的一种或几种，按其元素质量计，其总用量为所述净化材料成品质量的0.001％～10％。A further technical solution is that the porous adsorbent material is one or more of zeolite, silica gel, alumina, activated carbon and polydivinylbenzene; the total amount of the porous adsorbent material is the purification material. 0.1% to 30% of the quality of the finished product; the noble metal includes one or more of platinum, palladium, rhodium, iridium, gold and rare earth metal ruthenium, and the total amount thereof is the finished product of the purification material according to the elemental mass thereof. 0.001% to 10% of the mass.
优选地，所述的多孔吸附材料为沸石和氧化铝；所述的多孔材料的总用量最佳为0.5％～10％；所述的贵金属其总用量为所述净化材料成品质量的最佳为0.05％～1％。Preferably, the porous adsorbent material is zeolite and alumina; the total amount of the porous material is preferably 0.5% to 10%; the total amount of the precious metal is the best quality of the finished product of the purified material. 0.05% to 1%.
其进一步技术方案为：所述贵金属活性组分来源于贵金属单质、贵金属氧化物、贵金属配合物或贵金属无机盐中的任意一种或者至少两种的混合物；所述的稀土金属铈来源于氧化铈、氯化铈、硫酸铈、硝酸铈、硝酸铈铵中的一种 或者至少两种的混合物。A further technical solution is that the noble metal active component is derived from any one of a noble metal element, a noble metal oxide, a noble metal complex or a noble metal inorganic salt or a mixture of at least two; the rare earth metal cerium is derived from cerium oxide And one or a mixture of at least two of cerium chloride, cerium sulfate, cerium nitrate, ammonium cerium nitrate.
其进一步技术方案为：所述氧化物为氧化铂、氧化钯、氧化铑、氧化钌、氧化金或氧化铈；所述贵金属无机盐为氯化铂、氯化钯、氯化钯、氯化钌、氯化金或氯化铈或硫酸铈或硝酸铈或硝酸铈铵；所述贵金属配合物为氯铂酸钾、氯铂酸或氯铂酸氢钾。A further technical solution is that the oxide is platinum oxide, palladium oxide, cerium oxide, cerium oxide, gold oxide or cerium oxide; the noble metal inorganic salt is platinum chloride, palladium chloride, palladium chloride or cerium chloride. , gold chloride or barium chloride or barium sulfate or barium nitrate or ammonium cerium nitrate; the noble metal complex is potassium chloroplatinate, chloroplatinic acid or potassium chloroplatinate.
其进一步技术方案为：所述杀菌活性组分为含有银、锌或铜物质中的一种或几种，按其元素质量计总用量为所述净化材料成品质量的0.01％～20％。A further technical solution is that the bactericidal active component is one or more of silver, zinc or copper materials, and the total amount is 0.01% to 20% of the mass of the purified material according to the element mass.
优选地，所述杀菌活性组分按其元素质量计总用量为所述净化材料成品质量的0.05％～5％。Preferably, the bactericidal active component is used in an amount of 0.05% to 5% by mass of the element of the purified material.
其进一步技术方案为：所述杀菌活性组分中的铜来源于硝酸铜或氯化铜或硫酸铜或氧化铜；银来源于硝酸银或氧化银；锌来源于硝酸锌或氯化锌或氧化锌；所述的高分子材料包括聚酯、聚乙烯、聚丙烯和尼龙中的一种或几种。A further technical solution is that the copper in the bactericidal active component is derived from copper nitrate or copper chloride or copper sulfate or copper oxide; silver is derived from silver nitrate or silver oxide; zinc is derived from zinc nitrate or zinc chloride or oxidized Zinc; the polymer material includes one or more of polyester, polyethylene, polypropylene and nylon.
其进一步技术方案为：所述步骤三，还包括以下内容：甲醛催化氧化活性组分与杀菌活性组分先混合均匀，然后负载在所述的载体材料上，其后再与高分子材料复合制成纤维。A further technical solution is as follows: the third step further comprises the following: the formaldehyde catalytic oxidation active component and the bactericidal active component are first uniformly mixed, and then supported on the carrier material, and then combined with the polymer material. Fibres.
其进一步技术方案为：所述步骤三，还包括以下内容：分别将甲醛催化氧化活性组分和杀菌活性组分与载体材料复合，再将两种复合的载体材料混合。A further technical solution is as follows: the third step further comprises the following: compounding the catalytic oxidation active component and the bactericidal active component with the carrier material respectively, and then mixing the two composite carrier materials.
其进一步技术方案为：负载有甲醛催化氧化及杀菌材料的载体材料在高分子材料融熔过程中加入，或在喷丝过程中复合在纤维表面，或在纤维熔喷完成后再复合在纤维表面。The further technical solution is that the carrier material loaded with the formaldehyde catalytic oxidation and the sterilizing material is added during the melting process of the polymer material, or is compounded on the fiber surface during the spinning process, or is compounded on the fiber surface after the fiber melt-blown is completed. .
其进一步技术方案为：负载有甲醛催化氧化及杀菌活性组分的纤维通过针 刺或水刺、热压处理等工艺加工成无纺布材料，从而制成具有催化氧化甲醛和杀菌功能的净化新材料。The further technical scheme is: the fiber loaded with the catalytic oxidation of formaldehyde and the sterilizing active component is processed into a non-woven material by a needle punching or hydroentangling, hot pressing treatment, etc., thereby preparing a new purification product with catalytic oxidation of formaldehyde and sterilization function. material.
本申请与现有技术相比的有益效果是：The beneficial effects of the present application compared to the prior art are:
1、效率高：负载有甲醛催化氧化活性成分的载体颗粒紧密排列在纤维的表面，载体颗粒物分布均匀且覆盖率极高，载体颗粒良好地固定于纤维材料的表面，不易脱落。室温条件下甲醛去除率接近100％，可以把甲醛完全氧化为无毒无害的二氧化碳和水，同时杀菌效率高。细菌对复合纤维无耐药性，抗菌效果高达99％，且成本低；1. High efficiency: The carrier particles loaded with formaldehyde catalytic oxidation active components are closely arranged on the surface of the fiber, the carrier particles are uniformly distributed and the coverage is extremely high, and the carrier particles are well fixed on the surface of the fiber material, and are not easy to fall off. The formaldehyde removal rate is close to 100% at room temperature, which can completely oxidize formaldehyde to non-toxic and harmless carbon dioxide and water, and has high sterilization efficiency. The bacteria have no resistance to the composite fiber, the antibacterial effect is as high as 99%, and the cost is low;
2、稳定性好：在环境条件发生较大改变时，如湿度，甲醛浓度变化时，甲醛去除率仍然达到98％以上。且对于低浓度甲醛去除具有较明显效果；2. Good stability: When the environmental conditions change greatly, such as humidity and formaldehyde concentration change, the formaldehyde removal rate still reaches 98%. And has a significant effect on low concentration of formaldehyde removal;
3、制备工艺简单、制备条件温和：催化剂的制备过程对设备要求不高，程序较简单；3. The preparation process is simple and the preparation conditions are mild: the preparation process of the catalyst is not high on the equipment, and the procedure is relatively simple;
4、低成本：贵金属催化剂含量低，甲醛去除效率高，且长期使用，可有效降低贵金属的使用成本。且载体材料和纤维结合，能有效提高对有机物吸附容量，为甲醛的吸附提供了良好的条件，从而有利于甲醛的去除；4, low cost: low precious metal catalyst content, high formaldehyde removal efficiency, and long-term use, can effectively reduce the cost of precious metals. The combination of the carrier material and the fiber can effectively increase the adsorption capacity of the organic matter, and provides favorable conditions for the adsorption of formaldehyde, thereby facilitating the removal of formaldehyde;
5、环保、节能、使用范围广：甲醛催化氧化及杀菌材料制备过程中能量消耗低，使用中不需要外界给与光源和热源，实现甲醛在室温条件下的完全催化氧化。5, environmental protection, energy saving, a wide range of use: formaldehyde catalytic oxidation and sterilization materials in the preparation process of low energy consumption, the use of external light source and heat source is not required, to achieve complete catalytic oxidation of formaldehyde at room temperature.
下面结合附图和具体实施例对本申请作进一步描述。The present application is further described below in conjunction with the accompanying drawings and specific embodiments.
附图说明DRAWINGS
图1为具有催化氧化甲醛和杀菌功能的净化新材料的制备方法的流程图。1 is a flow chart of a method for preparing a purified new material having catalytic oxidation of formaldehyde and a bactericidal function.
具体实施方式detailed description
为了更充分理解本申请的技术内容，下面结合具体实施例对本申请的技术方案进一步介绍和说明，但不局限于此。In order to more fully understand the technical content of the present application, the technical solutions of the present application are further described and illustrated in conjunction with the specific embodiments, but are not limited thereto.
如图1所示的具体实施例，本申请公开了具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，包括以下步骤：As shown in the specific embodiment shown in Figure 1, the present application discloses a method for preparing a purified new material having catalytic oxidation of formaldehyde and a bactericidal function, comprising the following steps:
步骤一，以多孔吸附材料为载体；Step one, using a porous adsorbent material as a carrier;
步骤二，将具有催化氧化甲醛功能的贵金属、稀土金属材料、具有杀菌活性组分的含银、锌或铜的物质负载在所述的载体材料；Step 2, supporting a noble metal having a function of catalytic oxidation of formaldehyde, a rare earth metal material, a substance containing silver, zinc or copper having a bactericidal active component on the carrier material;
步骤三，将所述的负载有活性功能组分的载体材料与高分子材料复合制成纤维；Step 3, combining the carrier material loaded with the active functional component with the polymer material to form a fiber;
步骤四，将所述纤维加工成无纺布，完成净化材料的制作。In the fourth step, the fiber is processed into a non-woven fabric to complete the preparation of the purified material.
本申请采用以沸石、硅胶、氧化铝、活性碳、聚二乙烯基苯等多孔吸附材料中的一种或几种为载体；配置贵金属(铂、钯、铑、钌、金)和稀土金属(铈)中的一种或几种化合物的混合水溶液，再将载体与混合水溶液混合均匀，制得混合物；将混合物晶化处理，待晶化结束后，经分离、洗涤、干燥，即制备得到所述的负载催化氧化甲醛活性成分的改性载体材料；配置含银、锌或铜中的一种或几种的混合溶液，再将所述的载体材料加入到混合溶液中，将混合物晶化处理，待晶化处理完成后再经分离、洗涤、干燥，即制得杀菌功能的改性载体材料。The present application adopts one or more of porous adsorbing materials such as zeolite, silica gel, alumina, activated carbon and polydivinylbenzene as a carrier; and arranges precious metals (platinum, palladium, rhodium, iridium, gold) and rare earth metals ( a mixed aqueous solution of one or more compounds in 铈), and then uniformly mixing the carrier and the mixed aqueous solution to prepare a mixture; crystallization treatment of the mixture, after separation, washing, drying, and preparation a modified support material for catalytically oxidizing an active ingredient of formaldehyde; a mixed solution containing one or more of silver, zinc or copper, and then adding the support material to a mixed solution to crystallize the mixture After the crystallization treatment is completed, it is separated, washed, and dried to obtain a modified carrier material having a bactericidal function.
将上述改性载体材料及助剂按一定比例混合加入到融熔的聚酯、聚乙烯、聚丙烯或尼龙等材料中一起喷成纤维丝，或在喷丝过程中复合在纤维表面；将 上述复合纤维经过针刺或水刺、热压处理，制成无纺布，从而制成同时具有催化氧化甲醛和杀菌功能的净化新材料。Adding the above modified carrier material and auxiliary agent to a certain proportion of the melted polyester, polyethylene, polypropylene or nylon to be sprayed into the fiber, or compounded on the surface of the fiber during the spinning process; The composite fiber is subjected to needle punching or hydroentangling and hot pressing treatment to form a non-woven fabric, thereby preparing a new purification material which simultaneously has catalytic oxidation of formaldehyde and a sterilizing function.
其中，贵金属活性组分来源于贵金属单质、贵金属氧化物、贵金属配合物或贵金属无机盐中的任意一种或者至少两种的混合物。所述的稀土金属活性组分铈来源于氧化铈、氯化铈、硫酸铈、硝酸铈、硝酸铈铵中的一种。Wherein the precious metal active component is derived from any one of a noble metal element, a noble metal oxide, a noble metal complex or a noble metal inorganic salt or a mixture of at least two. The rare earth metal active component cerium is derived from one of cerium oxide, cerium chloride, cerium sulfate, cerium nitrate, and cerium ammonium nitrate.
其中，氧化物为氧化铂、氧化钯、氧化铑、氧化钌、氧化金或氧化铈；所述无机盐为氯化铂、氯化钯、氯化钯、氯化钌、氯化金或氯化铈或硫酸铈或硝酸铈或硝酸铈铵；所述配合物为氯铂酸钾、氯铂酸或氯铂酸氢钾(铂/钯/铑/钌/金)。Wherein the oxide is platinum oxide, palladium oxide, cerium oxide, cerium oxide, gold oxide or cerium oxide; the inorganic salt is platinum chloride, palladium chloride, palladium chloride, cerium chloride, gold chloride or chlorinated Barium or barium sulfate or barium nitrate or ammonium cerium nitrate; the complex is potassium chloroplatinate, chloroplatinic acid or potassium chloroplatinate (platinum/palladium/iridium/ruthenium/gold).
其中，假设净化材料成品的质量以100％计，所负载的铂/钯/铑/钌/金/铈化合物中的一种或几种按其元素总质量计，则活性组分的质量百分比0.005-10％，最佳为0.01％～1％。Wherein, assuming that the mass of the purified material is 100%, one or more of the supported platinum/palladium/ruthenium/rhenium/gold/ruthenium compounds are 0.005 by mass of the active component. -10%, preferably 0.01% to 1%.
其中，抗菌活性组分中铜来源于硝酸铜/氯化铜/硫酸铜，银来源于硝酸银/氧化银，锌来源于硝酸锌/氯化锌。假设净化材料成品的质量以100％计，铜银锌化合物的一种或几种的元素总质量百分比为0.01％～10％，最佳为0.05％～5％。Among them, copper in the antibacterial active component is derived from copper nitrate/copper chloride/copper sulfate, silver is derived from silver nitrate/silver oxide, and zinc is derived from zinc nitrate/zinc chloride. Assuming that the quality of the finished product of the purified material is 100%, the total mass percentage of one or more elements of the copper-silver-zinc compound is 0.01% to 10%, preferably 0.05% to 5%.
其中，晶化温度为80-160℃，晶化时间为1-24h小时。烘箱恒定干燥温度为80℃，2h。Among them, the crystallization temperature is 80-160 ° C, and the crystallization time is 1-24 h hours. The oven was oven dried at 80 ° C for 2 h.
其中，熔融过程中的助剂包括粘结剂和分散液体等，粘结剂为乙烯醋酸乙烯共聚物(EVA)或丙烯酸中的一种，优选丙烯酸。分散液体为抗静电油，银离子抗电油，磷酸酯，蜡，植物油中的一种，优选磷酸酯。混合物熔融温度下被注入的温度为300℃。Among them, the auxiliary agent in the melting process includes a binder and a dispersion liquid, and the binder is one of ethylene vinyl acetate copolymer (EVA) or acrylic acid, preferably acrylic acid. The dispersion liquid is one of an antistatic oil, a silver ion resistant electric oil, a phosphate ester, a wax, and a vegetable oil, preferably a phosphate ester. The temperature at which the mixture was injected at the melting temperature was 300 °C.
其中，具体实施步骤为将复合纤维铺放于转动的铺网帘上，形成1-100mm厚的混合纤维网，其中铺网帘的目数为50目。再将复合纤维进行针刺或水刺、热压处理。所述热压时间为1-30min，热压温度为90-200℃。Wherein, the specific implementation step is to lay the composite fiber on the rotating mesh curtain to form a mixed fiber web of 1-100 mm thickness, wherein the mesh curtain has a mesh number of 50 mesh. The composite fiber is then subjected to needle punching or hydroentangling and hot pressing. The hot pressing time is 1-30 min, and the hot pressing temperature is 90-200 °C.
本申请的具体实施例的制备方法具体包括以下内容：The preparation method of the specific embodiment of the present application specifically includes the following contents:
实施例1Example 1
配制元素Pt含量为0.1克的氯化铂、元素Ag含量为0.2克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu含量为0.5克的硝酸铜溶于水形成混合溶液，然后将100g沸石前驱体与混合水溶液混合均匀，得到混合物；再在100℃条件下将混合物晶化处理2h，制备得到同时负载有催化氧化甲醛的活性组分和杀菌功能的沸石颗粒；然后将880g聚酯纤维和20g磷酸酯放于转速为2500转/min的开松机内，开松分散处理，随后按其铂元素质量百分比0.02％加入所述负载有甲醛催化氧化及杀菌功能的沸石颗粒，使沸石与纤维在290℃条件下充分融熔混合，再通过喷丝头将合成纤维熔融抽丝挤出。然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为100℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切、制成去除甲醛杀菌的滤网。Formulating elemental platinum having a Pt content of 0.1 g, silver nitrate having an elemental Ag content of 0.2 g, zinc nitrate having an elemental Zn content of 0.3 g, and copper nitrate having an elemental Cu content of 0.5 g dissolved in water to form a mixed solution, and then 100 g of the zeolite precursor is uniformly mixed with the mixed aqueous solution to obtain a mixture; and the mixture is further subjected to crystallization treatment at 100 ° C for 2 hours to prepare zeolite particles which are simultaneously loaded with the active component of catalytic oxidation of formaldehyde and a bactericidal function; then 880 g of polyester is prepared. The fiber and 20g of phosphate ester were placed in a spinning machine with a rotation speed of 2500 rpm, and the dispersion treatment was carried out, and then the zeolite particles loaded with the catalytic oxidation and sterilization function of formaldehyde were added to the 0.02% by mass of the platinum element to make the zeolite. The fiber is thoroughly melted and mixed at 290 ° C, and the synthetic fiber is melt-spun and extruded through a spinneret. Then, a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded, cut, and made into a filter for removing formaldehyde sterilization.
实施例2Example 2
配制元素Rh含量为0.1克的氯化铑、元素Ag含量为0.2克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu含量为0.5克的硝酸铜溶于水形成混合溶液，然后将100g沸石前驱体与混合水溶液混合均匀，得到混合溶液。再在100℃条件下将混合溶液晶化处理，制备得到负载有催化剂的沸石颗粒。然后将880g聚酯纤维和20g磷酸酯放于转速为2500转/min的开松机内，开松分散处理，再通过喷丝 头将合成纤维熔融抽丝挤出。随后将负载有催化剂及杀菌剂的沸石颗粒按铑元素质量百分比0.02％喷涂至熔融的纤维表面。然后在数目为50目的转动铺网帘上形成2mm后的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为100℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网。Formulating cerium chloride having a Rh content of 0.1 g, silver nitrate having an elemental Ag content of 0.2 g, zinc nitrate having an elemental Zn content of 0.3 g, and copper nitrate having an elemental Cu content of 0.5 g dissolved in water to form a mixed solution, and then 100 g of the zeolite precursor was uniformly mixed with the mixed aqueous solution to obtain a mixed solution. Further, the mixed solution was crystallized at 100 ° C to prepare zeolite particles loaded with the catalyst. Then, 880 g of polyester fiber and 20 g of phosphate ester were placed in an opener at a rotation speed of 2,500 rpm, opened and dispersed, and the synthetic fiber was melt-spun and extruded through a spinneret. The zeolite particles loaded with the catalyst and the bactericide were then sprayed onto the surface of the molten fiber at a mass percentage of cerium of 0.02%. Then, a mixed fiber web of 2 mm is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
实施例3Example 3
配制元素Pd含量为0.05克的氯化钯和元素Pt含量为0.05的氯化铂、元素Ag含量为0.2克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu的含量为0.5克的硝酸铜溶于水形成混合溶液，然后将改性后的100g沸石前驱体与混合水溶液混合均匀，得到混合溶液，再在100℃条件下将混合溶液晶化处理，制备得到同时负载催化氧化甲醛的活性组分和杀菌功能的沸石颗粒；然后将790g的聚酯纤维和10g的磷酸酯放于转速为2500转/min的开松机内，开松分散处理，随后将负载有催化剂及杀菌剂的沸石颗粒按铂和钯元素总质量百分比0.02％加入负载有催化剂的沸石颗粒，使沸石与纤维在300℃条件下充分融解混合；再通过喷丝头将合成纤维熔融抽丝挤出；然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为110℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网。The preparation element has a Pd content of 0.05 g of palladium chloride and a platinum chloride having an elemental Pt content of 0.05, a silver nitrate having an elemental Ag content of 0.2 g, a zinc nitrate having an elemental Zn content of 0.3 g, and an elemental Cu content of 0.5 g. The copper nitrate is dissolved in water to form a mixed solution, and then the modified 100 g of the zeolite precursor is uniformly mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C to prepare a simultaneous catalytic oxidation of formaldehyde. Active component and bactericidal function of zeolite particles; then 790g of polyester fiber and 10g of phosphate ester are placed in a 2500 rev / min opener, opened and dispersed, and then loaded with catalyst and fungicide The zeolite particles are added to the catalyst-loaded zeolite particles at a total mass percentage of 0.02% of the platinum and palladium elements, so that the zeolite and the fibers are thoroughly melted and mixed at 300 ° C; and the synthetic fibers are melt-spun and extruded through a spinneret; A 2mm thick mixed fiber web is formed on the 50-mesh rotating screen curtain; the mixed fiber web is subjected to needle punching and hot pressing treatment, wherein the hot pressing time is 30 min, and the hot pressing temperature is 110 ° C. Nonwovens prepared; Finally, the non-woven material is folded, cut, removing the filter is made of formaldehyde sterilization.
实施例4Example 4
配制元素Au的含量为0.1克的氯金酸和元素Ce的含量为0.3克的硝酸铈、元素Ag含量为0.2克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu的含量为0.5克的硝酸铜溶于水形成混合溶液，然后将改性后的100g沸石前驱体与混合水溶 液混合均匀，得到混合溶液，再在100℃条件下将混合溶液晶化处理，制备得到同时负载催化氧化甲醛的活性组分和杀菌功能的沸石颗粒，然后将890g的聚酯纤维和10g的磷酸酯放于转速为2500转/min的开松机内，开松分散处理，随后随后将负载有催化剂及杀菌剂的沸石颗粒按金元素质量百分比0.02％加入负载有催化剂的沸石颗粒，使沸石与纤维在320℃条件下充分融熔混合，再通过喷丝头将合成纤维熔融抽丝挤出。然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为120℃，制备得到无纺布材料，最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网，分析认为，一方面是由于高比表面的CeO2形成高氧化态金属离子增强了甲醛的吸附能力，另一方面是由于纳米效应，高比表面积的CeO2可以提供更多的氧空位，并形成Au-Ce的共轭效应，氧分子在其上面被转化为活跃的物种参与反应当中，因而具有较高甲醛催化活性。The content of the preparation element Au is 0.1 g of chloroauric acid and the element Ce is 0.3 g of cerium nitrate, the elemental Ag content is 0.2 g of silver nitrate, the elemental Zn content is 0.3 g of zinc nitrate, and the element Cu content is 0.5. The gram of copper nitrate is dissolved in water to form a mixed solution, and then the modified 100 g of the zeolite precursor is mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C to prepare a simultaneous catalytic oxidation. The active component of formaldehyde and the granulating zeolite particles, then 890 g of polyester fiber and 10 g of phosphate are placed in an opener at a speed of 2500 rpm, opened and dispersed, and then loaded with a catalyst and The zeolite particles of the bactericide are added to the catalyst-loaded zeolite particles at a mass percentage of 0.02% of the gold element, the zeolite and the fibers are sufficiently melt-mixed at 320 ° C, and the synthetic fibers are melt-spun and extruded through a spinneret. Then, a mixed web of 2 mm thick was formed on a rotating screen of 50 mesh; the mixed fiber web was subjected to needle punching and hot pressing, wherein the hot pressing time was 30 min, the hot pressing temperature was 120 ° C, and the non-woven fabric was prepared. Cloth material, finally, the non-woven material is folded and sheared to make a filter for removing formaldehyde sterilization. According to the analysis, on the one hand, the formation of highly oxidized metal ions by CeO2 with high specific surface enhances the adsorption capacity of formaldehyde. On the other hand, due to the nano-effect, CeO2 with high specific surface area can provide more oxygen vacancies and form a conjugation effect of Au-Ce, on which oxygen molecules are converted into active species to participate in the reaction, and thus have higher Formaldehyde catalytic activity.
实施例5Example 5
配制元素Rh的含量为0.05克的氯化铑和元素Pd的含量为0.05克氯化钯与100g聚二乙烯基苯混合处理制备得到负载有甲醛催化氧化的载体颗粒；另取元素Ag含量为0.2克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu含量为0.5克的硝酸铜溶于水形成混合溶液，然后将100g改性后的沸石前驱体与混合水溶液混合均匀，得到混合溶液，再在100℃条件下将混合溶液晶化处理，制备得到负载有杀菌活性成分的沸石颗粒。然后将790g的聚酯纤维和10g的磷酸酯放于转速为2500转/min的开松机内，开松分散处理，再通过喷丝头将合成纤维熔融抽丝挤出。随后将负载有甲醛催化氧化活性成分的聚二乙烯基苯颗粒与负载有上述杀菌活性成分的沸石颗粒按1：1的比例混合，再按钯和铑的总质量百分比0.01％喷涂在纤维表面；然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网； 再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为100℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网。The carrier element Rh content is 0.05 g of cerium chloride and the element Pd content is 0.05 g of palladium chloride and 100 g of polydivinylbenzene are mixed to prepare a carrier particle loaded with formaldehyde-catalyzed oxidation; and the elemental Ag content is 0.2. a silver nitrate, a zinc nitrate having an elemental Zn content of 0.3 g, a copper nitrate having an elemental Cu content of 0.5 g dissolved in water to form a mixed solution, and then 100 g of the modified zeolite precursor and the mixed aqueous solution are uniformly mixed to obtain a mixed solution. Then, the mixed solution is crystallized at 100 ° C to prepare zeolite particles loaded with the bactericidal active ingredient. Then, 790 g of the polyester fiber and 10 g of the phosphate ester were placed in an opener at a rotation speed of 2,500 rpm, and the dispersion treatment was carried out, and the synthetic fiber was melt-spun and extruded through a spinneret. Subsequently, the polydivinylbenzene particles loaded with the formaldehyde catalytically oxidizing active ingredient are mixed with the zeolite particles loaded with the above bactericidal active ingredient in a ratio of 1:1, and then sprayed on the surface of the fiber at a total mass percentage of 0.01% of palladium and ruthenium; Then, a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
实施例6Example 6
配制元素Pt含量为0.1克的氯化铂与100g聚二乙烯基苯混合处理制备得到负载有催化剂的载体颗粒；另取元素Ag含量为0.3克的硝酸银、元素Zn含量为0.2克的硝酸锌、元素Cu含量为0.5克的硝酸铜溶于水形成混合溶液，然后将100g改性后的沸石前驱体与混合水溶液混合均匀，得到混合溶液，再在100℃条件下将混合溶液晶化处理，制备得到负载有杀菌活性成分的沸石颗粒；然后将790g的聚酯纤维和10g的磷酸酯放于转速为2500转/min的开松机内，开松分散处理，再通过喷丝头将合成纤维熔融抽丝挤出。随后将负载有催化氧化甲醛的活性成分聚二乙烯基苯颗粒与负载有上述杀菌活性成分的沸石颗粒按1：1的比例混合，随后将负载有催化剂及杀菌剂的沸石颗粒按铂元素质量百分比0.01％喷涂在纤维表面。然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为100℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网。The catalyst particles are prepared by mixing platinum chloride with a Pt content of 0.1 g and 100 g of polydivinylbenzene; and silver nitrate having an elemental Ag content of 0.3 g and zinc nitrate having an elemental Zn content of 0.2 g are prepared. The copper nitrate having an elemental Cu content of 0.5 g is dissolved in water to form a mixed solution, and then 100 g of the modified zeolite precursor is uniformly mixed with the mixed aqueous solution to obtain a mixed solution, and then the mixed solution is crystallized at 100 ° C. Preparing the zeolite particles loaded with the bactericidal active ingredient; then placing 790 g of the polyester fiber and 10 g of the phosphate ester in an opener rotating at 2500 rpm, opening and dispersing, and then passing the synthetic fiber through the spinneret Melt spinning and extrusion. Subsequently, the active ingredient polydivinylbenzene particles loaded with catalytic oxidation of formaldehyde are mixed with the zeolite particles loaded with the above bactericidal active ingredient in a ratio of 1:1, and then the zeolite particles loaded with the catalyst and the bactericide are mass% of the platinum element. 0.01% sprayed on the fiber surface. Then, a mixed web of 2 mm thick is formed on a rotating screen of 50 mesh; the mixed fiber web is subjected to needle punching and hot pressing, wherein the hot pressing time is 30 min, the hot pressing temperature is 100 ° C, and the non-woven fabric is prepared. Cloth material; Finally, the non-woven material is folded and cut to prepare a filter for removing formaldehyde sterilization.
实施例7Example 7
配制元素Pt含量为0.05克的氯化铂和元素Ru含量为0.05克的氯化钌与100g氧化铝分子筛混合处理制备得到负载有催化剂的载体颗粒；另取元素Ag含量为0.25克的硝酸银、元素Zn含量为0.3克的硝酸锌、元素Cu含量为0.3克的硝酸铜溶于水形成混合溶液，然后将100g改性后的沸石前驱体与混合水溶液混合均匀， 得到混合溶液，再在100℃条件下将混合溶液晶化处理，制备得到负载有杀菌活性成分的沸石颗粒；然后将790g的聚酯纤维和10g的磷酸酯放于转速为2500转/min的开松机内，开松分散处理，再通过喷丝头将合成纤维熔融抽丝挤出；随后将负载有甲醛催化氧化活性成分的氧化铝颗粒与负载有上述杀菌活性成分的沸石颗粒按1：1的比例混合，再按铂元素质量百分比0.01％喷涂在纤维表面；然后在数目为50目的转动铺网帘上形成2mm厚的混合纤维网；再将混合纤维网进行针刺、热压处理，其中热压时间为30min，热压温度为100℃，制备得到无纺布材料；最后，将无纺布材料进行折叠、剪切，制成去除甲醛杀菌的滤网。The catalyst particles are prepared by mixing platinum chloride with a Pt content of 0.05 g and ruthenium chloride with an elemental Ru content of 0.05 g and 100 g of alumina molecular sieve; and taking silver nitrate with an elemental Ag content of 0.25 g, The zinc nitrate having an elemental Zn content of 0.3 g and the copper nitrate having an elemental Cu content of 0.3 g are dissolved in water to form a mixed solution, and then 100 g of the modified zeolite precursor is mixed with the mixed aqueous solution to obtain a mixed solution, and then at 100 ° C. The mixed solution is crystallized to prepare zeolite particles loaded with the bactericidal active ingredient; then 790 g of the polyester fiber and 10 g of the phosphate ester are placed in an opener at a rotation speed of 2500 rpm, and the dispersion treatment is carried out. And then, the synthetic fiber is melt-spun and extruded through a spinneret; then, the alumina particles loaded with the formaldehyde-catalyzed active component are mixed with the zeolite particles loaded with the above-mentioned bactericidal active component in a ratio of 1:1, and then platinum is added. a percentage by mass of 0.01% was sprayed onto the surface of the fiber; then a 2 mm thick mixed web was formed on a 50-mesh rotating screen curtain; the mixed web was then needled, Pressure treatment, wherein pressing time is 30min, pressing temperature of 100 deg.] C, prepared nonwovens; Finally, the non-woven material is folded, cut, removing the filter is made of formaldehyde sterilization.
除甲醛反应的评价条件：原料为100ppm的甲醛/高纯空气混合气(21％O2+79％N2)，反应气体流量为100ml/min，反应温度25℃，室内环境湿度水平(RH 80％)气体体积空速为80000h-1，取反应1h时的点进行取样分析，不同催化剂的对比数据如下表所示：In addition to the evaluation conditions of formaldehyde reaction: the raw material is 100ppm formaldehyde/high purity air mixture (21%O2+79%N2), the reaction gas flow rate is 100ml/min, the reaction temperature is 25°C, and the indoor environmental humidity level (RH 80%) The gas volumetric space velocity is 80000h-1, and the point at which the reaction is taken for 1h is sampled and analyzed. The comparison data of different catalysts are shown in the following table:
甲醛去除率(％)Formaldehyde removal rate (%) 二氧化碳选择性(％)Carbon dioxide selectivity (%)
实施例1Example 1 100100 100100
实施例2Example 2 100100 100100
实施例3Example 3 100100 100100
实施例4Example 4 100100 100100
实施例5Example 5 100100 100100
实施例6Example 6 9999 9898
实施例7Example 7 9999 9898
从上表中可以看出，本申请所获得的除甲醛催化剂的甲醛脱除率在室温条件下去除率均大于99％，且二氧化碳的选择性达到98％以上；完成了本申请的目的。As can be seen from the above table, the formaldehyde removal rate of the formaldehyde-removing catalyst obtained in the present application is more than 99% at room temperature, and the selectivity of carbon dioxide is over 98%; the object of the present application is completed.
综上所述，本申请使负载有甲醛催化氧化活性成分和杀菌活性成分的载体材料与聚酯、聚乙烯、聚丙烯及尼龙等高分子材料结合，经过加温熔融，使活性组分和纤维键接，在纤维内外形成牢固的活性层，增大了材料的比表面积，有利于活性组分的分散，能够使甲醛与催化剂充分接触，对甲醛有良好的净化功能；同时使病菌与杀菌材料充分接触，快速杀灭病菌。In summary, the present application combines a carrier material loaded with a formaldehyde-catalyzed active ingredient and a bactericidal active ingredient with a polymer material such as polyester, polyethylene, polypropylene, and nylon, and is heated and melted to make the active component and the fiber. Bonding, forming a strong active layer inside and outside the fiber, increasing the specific surface area of the material, facilitating the dispersion of the active component, enabling the formaldehyde to fully contact with the catalyst, and having a good purifying function for formaldehyde; and simultaneously making the germ and the germicidal material Fully contact and quickly kill germs.
上述仅以实施例来进一步说明本申请的技术内容，以便于读者更容易理解，但不代表本申请的实施方式仅限于此，任何依本申请所做的技术延伸或再创造，均受本申请的保护。本申请的保护范围以权利要求书为准。The technical content of the present application is further described by way of example only, so as to be easier for the reader to understand, but the embodiment of the present application is not limited thereto, and any technical extension or re-creation made according to the application is subject to the present application. protection of. The scope of protection of this application is subject to the claims.

Claims (10)

  1. 具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，包括以下步骤：A method for preparing a new purification material having catalytic oxidation of formaldehyde and a bactericidal function, comprising the steps of:
    步骤一，以多孔吸附材料为载体；Step one, using a porous adsorbent material as a carrier;
    步骤二，将具有催化氧化甲醛功能的贵金属、稀土金属材料、具有杀菌活性组分的含银、锌或铜的物质负载在所述的载体材料；Step 2, supporting a noble metal having a function of catalytic oxidation of formaldehyde, a rare earth metal material, a substance containing silver, zinc or copper having a bactericidal active component on the carrier material;
    步骤三，将所述的负载有活性功能组分的载体材料与高分子材料复合制成纤维；Step 3, combining the carrier material loaded with the active functional component with the polymer material to form a fiber;
    步骤四，将所述纤维加工成无纺布，完成净化材料的制作。In the fourth step, the fiber is processed into a non-woven fabric to complete the preparation of the purified material.
  2. 根据权利要求1所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述的多孔吸附材料为沸石、硅胶、氧化铝、活性碳和聚二乙烯基苯中的一种或几种；所述的多孔吸附材料的总用量为所述净化材料成品质量的0.1％～30％；所述的贵金属包括铂、钯、铑、钌、金和稀土金属铈中的一种或几种，按其元素质量计，其总用量为所述净化材料成品质量的0.001％～10％。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilization function according to claim 1, wherein the porous adsorption material is zeolite, silica gel, alumina, activated carbon and polydivinylbenzene. One or more; the total amount of the porous adsorbent material is 0.1% to 30% of the mass of the purified material; the noble metal includes one of platinum, palladium, rhodium, iridium, gold and rare earth metal lanthanum One kind or several kinds, the total amount of the element is 0.001% to 10% of the quality of the finished product of the purified material.
  3. 根据权利要求2所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述贵金属活性组分来源于贵金属单质、贵金属氧化物、贵金属配合物或贵金属无机盐中的任意一种或者至少两种的混合物；所述的稀土金属铈来源于氧化铈、氯化铈、硫酸铈、硝酸铈、硝酸铈铵中的一种或者至少两种的混合物。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilizing function according to claim 2, wherein the noble metal active component is derived from a noble metal element, a noble metal oxide, a noble metal complex or a noble metal inorganic salt. Any one or a mixture of at least two; the rare earth metal cerium is derived from one of cerium oxide, cerium chloride, cerium sulfate, cerium nitrate, ammonium cerium nitrate or a mixture of at least two.
  4. 根据权利要求3所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述氧化物为氧化铂、氧化钯、氧化铑、氧化钌、氧化金或氧化铈；所述贵金属无机盐为氯化铂、氯化钯、氯化钯、氯化钌、氯化金或氯化铈或硫酸铈或硝酸铈或硝酸铈铵；所述贵金属配合物为氯铂酸钾、氯铂酸或氯铂酸氢钾。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilizing function according to claim 3, wherein the oxide is platinum oxide, palladium oxide, cerium oxide, cerium oxide, gold oxide or cerium oxide; The precious metal inorganic salt is platinum chloride, palladium chloride, palladium chloride, rhodium chloride, gold chloride or barium chloride or barium sulfate or barium nitrate or ammonium cerium nitrate; the noble metal complex is potassium chloroplatinate, Chloroplatinic acid or potassium chloroplatinate.
  5. 根据权利要求1所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述杀菌活性组分为含有银、锌或铜物质中的一种或几种，按其元素质量计总用量为所述净化材料成品质量的0.01％～20％。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilizing function according to claim 1, wherein the bactericidal active component is one or more of silver, zinc or copper, according to The total amount of the element mass meter is 0.01% to 20% of the mass of the purified material.
  6. 根据权利要求5所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述杀菌活性组分中的铜来源于硝酸铜或氯化铜或硫酸铜或氧化铜；银来源于硝酸银或氧化银；锌来源于硝酸锌或氯化锌或氧化锌；所述的高分子材料包括聚酯、聚乙烯、聚丙烯和尼龙中的一种或几种。The method according to claim 5, wherein the copper in the bactericidal active component is derived from copper nitrate or copper chloride or copper sulfate or copper oxide; Silver is derived from silver nitrate or silver oxide; zinc is derived from zinc nitrate or zinc chloride or zinc oxide; and the polymer material includes one or more of polyester, polyethylene, polypropylene and nylon.
  7. 根据权利要求1所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述步骤三，还包括以下内容：甲醛催化氧化活性组分与杀菌活性组分先混合均匀，然后负载在所述的载体材料上，其后再与高分子材料复合制成纤维。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilization function according to claim 1, wherein the step 3 further comprises the following: mixing the catalytically active component of the formaldehyde with the bactericidal active component first; Then, it is supported on the carrier material, and then composited with a polymer material to form a fiber.
  8. 根据权利要求7所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，所述步骤三，还包括以下内容：分别将甲醛催化氧化活性组分和杀菌活性组分与载体材料复合，再将两种复合的载体材料混合。The method for preparing a new purification material having catalytic oxidation of formaldehyde and a sterilization function according to claim 7, wherein the step 3 further comprises the following: respectively: catalytically oxidizing the active component and the bactericidal active component of the formaldehyde; The carrier material is compounded and the two composite carrier materials are combined.
  9. 根据权利要求1所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，负载有甲醛催化氧化及杀菌材料的载体材料在高分子材 料融熔过程中加入，或在喷丝过程中复合在纤维表面，或在纤维熔喷完成后再复合在纤维表面。The method for preparing a purified new material having catalytic oxidation of formaldehyde and a sterilizing function according to claim 1, wherein the carrier material loaded with formaldehyde catalytic oxidation and sterilizing material is added during the melting process of the polymer material, or is sprayed The wire is compounded on the surface of the fiber or composited on the surface of the fiber after the fiber is melt blown.
  10. 根据权利要求1所述的具有催化氧化甲醛和杀菌功能的净化新材料的制备方法，其特征在于，负载有甲醛催化氧化及杀菌活性组分的纤维通过针刺或水刺、热压处理等工艺加工成无纺布材料，从而制成具有催化氧化甲醛和杀菌功能的净化新材料。The method for preparing a new purification material with catalytic oxidation of formaldehyde and bactericidal function according to claim 1, characterized in that the fiber loaded with formaldehyde catalytic oxidation and sterilizing active component is subjected to acupuncture or hydroentangling, hot pressing treatment, etc. Processed into a non-woven material to produce a new purification material with catalytic oxidation of formaldehyde and bactericidal function.
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