WO2019001035A1 - Composite carrier, preparation method therefor and application thereof - Google Patents

Composite carrier, preparation method therefor and application thereof Download PDF

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Publication number
WO2019001035A1
WO2019001035A1 PCT/CN2018/079824 CN2018079824W WO2019001035A1 WO 2019001035 A1 WO2019001035 A1 WO 2019001035A1 CN 2018079824 W CN2018079824 W CN 2018079824W WO 2019001035 A1 WO2019001035 A1 WO 2019001035A1
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carrier
resin liquid
composite
adsorption
mechanical
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PCT/CN2018/079824
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French (fr)
Chinese (zh)
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刘若鹏
赵治亚
孙明娟
胡建景
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深圳光启高等理工研究院
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Publication of WO2019001035A1 publication Critical patent/WO2019001035A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • B01D53/46—Removing components of defined structure
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths

Definitions

  • the present invention relates to the field of materials, and more particularly to a composite carrier and a preparation method and application thereof.
  • the present invention uses a carbon-based carrier of carbon fiber, carbon fiber, activated carbon, and graphene as an adsorption carrier, or a combination of a carbon-based carrier and other carriers of alumina, silica, and titania as an adsorption carrier, and
  • the mechanical carrier with good mechanical strength combines to form a composite carrier, so that the prepared catalyst can achieve efficient removal of benzene pollutants, and at the same time, the gas channel is formed by the skeleton support of the mechanical carrier, which can effectively overcome the wear of the catalyst during long-term use, Loss and difficult to recycle, improve the life of the catalyst.
  • the invention provides a composite carrier comprising:
  • a mechanical carrier a mechanical carrier
  • an adsorption carrier a resin liquid
  • the mechanical carrier, the adsorption carrier, and the resin liquid have a mass ratio of 10 to 20: 0.1 to 20: 0.1 to 20.
  • the mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam.
  • the adsorption carrier includes a carbon-based carrier; the carbon-based carrier includes one or more of carbon fiber, activated carbon, and graphene.
  • the adsorption carrier further includes other carriers; the other carrier includes one or more of alumina, silica, and titania.
  • the resin liquid includes one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
  • the invention also provides a method of preparing a composite carrier comprising the following steps:
  • the adsorption carrier is mixed with the resin liquid to be configured to adsorb the carrier resin liquid; the adsorption carrier resin liquid is combined with the mechanical carrier; and cured and dried to obtain the composite carrier.
  • the mass ratio of the mechanical carrier, the adsorption carrier, and the resin liquid is from 10 to 20: 0.1 to 20: 0.1 to 20.
  • the adsorption carrier resin liquid is combined with the mechanical carrier by dipping, spraying or coating.
  • the mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam.
  • the adsorption carrier comprises a carbon-based support;
  • the carbon-based support comprises one or more of carbon fiber, activated carbon and graphene;
  • the adsorption carrier further includes other carriers; the other carrier includes one or more of alumina, silica, and titania.
  • the resin liquid includes one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
  • the invention also provides the use of the above composite support in a catalyst.
  • the composite carrier prepared by the method of the invention can combine the high specific surface area coating on the mechanical carrier with the honeycomb, the foam as the mechanical carrier, and jointly form the composite carrier of the catalyst, thereby imparting strong mechanical strength to the catalyst carrier and realizing the benzene. Efficient removal of pollutants, while effectively overcoming the problem of wear, loss and difficult recycling of the catalyst during long-term use.
  • the carbon-based carrier in the adsorption carrier is a core component for realizing low-temperature and high-efficiency removal of benzene-based pollutants, and in combination with other carriers, the heat conduction of the carrier in the strong exothermic and strong endothermic reaction can be further improved.
  • the mechanical carrier provides a channel for the gaseous pollutant to pass through the high adsorption carrier, on the one hand, ensuring smooth flow of the gaseous pollutant through the catalytic carrier, and on the other hand, ensuring that the catalyst is not easily lost.
  • the effective combination of the two supports effectively improves the selective removal of benzene pollutants by the catalyst and the service life of the catalyst.
  • the invention effectively combines a mechanical carrier having a certain mechanical strength with an adsorption carrier having a high adsorption effect to form a composite carrier, and realizes low-temperature and high-efficiency removal of benzene-based pollutants through an adsorption carrier having a carbon-based carrier, and simultaneously serves as a skeleton support through a mechanical carrier.
  • the specific preparation process is as follows:
  • 0.1 to 20 parts of the adsorption carrier is mixed with 0.1 to 20 parts of the resin liquid to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid is combined with 10 to 20 parts of the mechanical carrier by dipping, spraying or coating, and cured at room temperature.
  • the mechanical carrier comprises aluminum honeycomb, paper honeycomb, polymethacrylimide (PMI) foam and polyethylene terephthalate ( PET) one or more of the foam
  • the adsorption carrier may include not only a carbon-based carrier of carbon fiber, activated carbon, and graphene, but may also include other carriers of alumina, silica, and titania
  • the resin solution includes an epoxy resin solution One or more of a polyimide resin liquid and an isocyanate resin liquid.
  • adsorption carrier resin liquid 5 parts of activated carbon and 10 parts of epoxy resin were mixed to prepare adsorption carrier resin liquid, and then the adsorption carrier resin liquid was sprayed to 10 parts of mechanical carrier aluminum honeycomb, cured at room temperature for 12 hours, dried in an oven at 80 ° C. At 12 h, a composite vector was obtained.
  • 0.1 part of carbon fiber is mixed with 0.1 part of polyimide resin liquid to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid is combined with 10 parts of mechanical carrier paper honeycomb by dipping, and cured at room temperature for 10 hours, 70 ° C in an oven. After drying for 14 h, a composite carrier was obtained.
  • Example 1 benzene Activated carbon 85% 86% 42
  • Example 2 Toluene carbon fiber 87% 84% 40
  • Example 3 benzene Graphene and activated carbon 90% 87% 43
  • Example 4 Meta-xylene Carbon fiber and silicon oxide 89% 90% 39
  • Example 5 Toluene Activated carbon and titanium oxide 92% 91% 40
  • Example 6 Meta-xylene Graphene and alumina 90% 85% 41
  • the present invention can realize the selective removal of benzene pollutants by introducing a carbon-based carrier into the composite carrier, so that the prepared catalyst removal rate is as high as 92% and the selectivity is as high as 91%.
  • the selective and efficient removal of benzene pollutants is realized; in addition, the combination of the mechanical carrier and the high specific surface area adsorption carrier ensures smooth circulation of the gaseous pollutants while passing through the catalyst, and ensures that the catalyst is not easily lost, so that the catalyst is The number of regenerations is up to 43 times, which improves the service life of the catalyst and effectively overcomes the problems of wear, loss and difficult recovery of the catalyst during long-term use.
  • the catalyst prepared by the composite carrier of the invention can be applied to an air purifier, an air conditioner, a gas mask, a ventilation fan, etc., which can effectively improve the removal effect of the product on the benzene pollutants, reduce the pollution and harm to the environment and the human body, and can long-term use.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

A composite carrier, a preparation method therefor and application thereof. The composite material comprises: a mechanical carrier; an adsorption carrier; and a resin liquid. The mass ratio of the mechanical carrier to the adsorption carrier to the resin liquid is 10-20:0.1-20:0.1-20. The composite carrier prepared by means of the method can implement efficient removal of benzene-based pollutants by a composite carrier catalyst, and also effectively prolong the service life of the catalyst.

Description

一种复合载体及其制备方法和应用Composite carrier and preparation method and application thereof 技术领域Technical field
本发明涉及材料领域，更具体地，涉及一种复合载体及其制备方法和应用。The present invention relates to the field of materials, and more particularly to a composite carrier and a preparation method and application thereof.
背景技术Background technique
随着污染尤其是雾霾中的苯类污染日益严重，该污染对环境和人体健康造成很大伤害，因此，对苯类污染物的选择性去除变得至关重要，但是现有的载体催化剂通常适用于强吸热和强放热的催化重整反应，并未涉及对苯类污染物的选择性去除效果，并且现有催化剂在长期使用过程中易出现磨损、流失以及难回收等的问题，缩短了催化剂的使用寿命。With the increasing pollution of benzene in pollution, especially in smog, the pollution causes great harm to the environment and human health. Therefore, the selective removal of benzene pollutants becomes crucial, but the existing supported catalysts It is usually applied to the catalytic end-reaction of strong endothermic and strong exothermic. It does not involve the selective removal of benzene pollutants, and the existing catalysts are prone to wear, loss and difficult recycling during long-term use. , shortens the service life of the catalyst.
发明内容Summary of the invention
针对以上问题，本发明通过使用碳纤维、碳纤维、活性炭和石墨烯的碳基载体作为吸附载体，或碳基载体与氧化铝、氧化硅和氧化钛的其它载体的组合作为吸附载体，再与具有较好的机械强度的机械载体结合形成复合载体，使得制备的催化剂可以实现对苯类污染物的高效去除，同时通过机械载体的骨架支撑形成气体通道，能够有效克服催化剂在长期使用过程中的磨损、流失及难回收的问题，提高催化剂的使用寿命。In view of the above problems, the present invention uses a carbon-based carrier of carbon fiber, carbon fiber, activated carbon, and graphene as an adsorption carrier, or a combination of a carbon-based carrier and other carriers of alumina, silica, and titania as an adsorption carrier, and The mechanical carrier with good mechanical strength combines to form a composite carrier, so that the prepared catalyst can achieve efficient removal of benzene pollutants, and at the same time, the gas channel is formed by the skeleton support of the mechanical carrier, which can effectively overcome the wear of the catalyst during long-term use, Loss and difficult to recycle, improve the life of the catalyst.
本发明提供了一种复合载体，包括：The invention provides a composite carrier comprising:
机械载体；吸附载体；以及树脂液，其中，所述机械载体、所述吸附载体和所述树脂液的质量比为10～20:0.1～20:0.1～20。a mechanical carrier; an adsorption carrier; and a resin liquid, wherein the mechanical carrier, the adsorption carrier, and the resin liquid have a mass ratio of 10 to 20: 0.1 to 20: 0.1 to 20.
在上述复合载体中，所述机械载体包括铝蜂窝、纸蜂窝、聚甲基丙烯酰亚胺泡沫和聚对苯二甲酸乙二醇酯泡沫中的一种或多种。In the above composite carrier, the mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam.
在上述复合载体中，所述吸附载体包括碳基载体；所述碳基载体包括碳纤维、活性炭和石墨烯中的一种或多种。In the above composite carrier, the adsorption carrier includes a carbon-based carrier; the carbon-based carrier includes one or more of carbon fiber, activated carbon, and graphene.
在上述复合载体中，所述吸附载体还包括其它载体；所述其它载体包括氧化铝、氧化硅和氧化钛中的一种或多种。In the above composite carrier, the adsorption carrier further includes other carriers; the other carrier includes one or more of alumina, silica, and titania.
在上述复合载体中，所述树脂液包括环氧树脂液、聚酰亚胺树脂液和异氰酸酯树脂液中的一种或多种。In the above composite carrier, the resin liquid includes one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
本发明还提供了一种制备复合载体的方法，包括以下步骤：The invention also provides a method of preparing a composite carrier comprising the following steps:
将吸附载体与树脂液混合，配置成吸附载体树脂液；将所述吸附载体树脂液与机械载体结合；以及固化、干燥，得到所述复合载体。The adsorption carrier is mixed with the resin liquid to be configured to adsorb the carrier resin liquid; the adsorption carrier resin liquid is combined with the mechanical carrier; and cured and dried to obtain the composite carrier.
在上述方法中，所述机械载体、所述吸附载体和所述树脂液的质量比为10～20:0.1～20:0.1～20。In the above method, the mass ratio of the mechanical carrier, the adsorption carrier, and the resin liquid is from 10 to 20: 0.1 to 20: 0.1 to 20.
在上述方法中，通过浸渍、喷淋或涂覆的方式将所述吸附载体树脂液与所述机械载体结合。In the above method, the adsorption carrier resin liquid is combined with the mechanical carrier by dipping, spraying or coating.
在上述方法中，所述机械载体包括铝蜂窝、纸蜂窝、聚甲基丙烯酰亚胺泡沫和聚对苯二甲酸乙二醇酯泡沫中的一种或多种。In the above method, the mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam.
在上述方法中，所述吸附载体包括碳基载体；所述碳基载体包括碳纤维、活性炭和石墨烯中的一种或多种；In the above method, the adsorption carrier comprises a carbon-based support; the carbon-based support comprises one or more of carbon fiber, activated carbon and graphene;
在上述方法中，所述吸附载体还包括其它载体；所述其它载体包括氧化铝、氧化硅和氧化钛中的一种或多种。In the above method, the adsorption carrier further includes other carriers; the other carrier includes one or more of alumina, silica, and titania.
在上述方法中，所述树脂液包括环氧树脂液、聚酰亚胺树脂液和异氰酸酯树脂液中的一种或多种。In the above method, the resin liquid includes one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
本发明还提供了上述复合载体在催化剂中的应用。The invention also provides the use of the above composite support in a catalyst.
通过本发明的方法制备的复合载体，通过以蜂窝、泡沫为机械载体，结合机械载体上的高比表面积涂层，共同构成催化剂的复合载体，赋予催化剂载体强机械强度的同时，能够实现对苯类污染物的高效去除，同时有效克服催化剂在长期使用过程中的磨损、流失及难回收的问题。The composite carrier prepared by the method of the invention can combine the high specific surface area coating on the mechanical carrier with the honeycomb, the foam as the mechanical carrier, and jointly form the composite carrier of the catalyst, thereby imparting strong mechanical strength to the catalyst carrier and realizing the benzene. Efficient removal of pollutants, while effectively overcoming the problem of wear, loss and difficult recycling of the catalyst during long-term use.
在该复合载体中，吸附载体中的碳基载体是实现低温、高效去除苯类污染物的核心成分，与其它载体的结合使用，可进一步提高载体在强放热和强吸热反应中的导热性；机械载体作为骨架支撑，为气态污染物通过高吸附载体提供通道，一方面保证气态污染物通过催化载体时流通顺畅，另一方面保证催化剂不易流失。两种载体的有效结合有效提高了催化剂对苯类污染物选择性去除效 果以及催化剂的使用寿命。In the composite carrier, the carbon-based carrier in the adsorption carrier is a core component for realizing low-temperature and high-efficiency removal of benzene-based pollutants, and in combination with other carriers, the heat conduction of the carrier in the strong exothermic and strong endothermic reaction can be further improved. As a skeleton support, the mechanical carrier provides a channel for the gaseous pollutant to pass through the high adsorption carrier, on the one hand, ensuring smooth flow of the gaseous pollutant through the catalytic carrier, and on the other hand, ensuring that the catalyst is not easily lost. The effective combination of the two supports effectively improves the selective removal of benzene pollutants by the catalyst and the service life of the catalyst.
具体实施方式Detailed ways
下面的实施例可以使本领域技术人员更全面地理解本发明，但不以任何方式限制本发明。The following examples are intended to provide a more complete understanding of the invention, and are not intended to limit the invention in any way.
本发明将具有一定机械强度的机械载体与具有高吸附效果的吸附载体有效结合形成复合载体，通过具有碳基载体的吸附载体实现低温、高效去除苯类污染物，同时通过机械载体作为骨架支撑，为气态污染物通过吸附载体提供通道，使得制备的催化剂具有对苯类污染物的选择性去除效果，并且克服催化剂在长期使用过程中的磨损、流失及难回收的问题，提高了催化剂的使用寿命，按重量份计，具体制备过程如下：The invention effectively combines a mechanical carrier having a certain mechanical strength with an adsorption carrier having a high adsorption effect to form a composite carrier, and realizes low-temperature and high-efficiency removal of benzene-based pollutants through an adsorption carrier having a carbon-based carrier, and simultaneously serves as a skeleton support through a mechanical carrier. Providing channels for the gaseous pollutants through the adsorption carrier, so that the prepared catalyst has the selective removal effect on the benzene pollutants, and overcomes the problems of wear, loss and difficult recovery of the catalyst during long-term use, thereby improving the service life of the catalyst. According to the parts by weight, the specific preparation process is as follows:
将0.1～20份吸附载体与0.1～20份树脂液混合，配制成吸附载体树脂液，然后采用浸渍、喷淋或涂覆的方式将吸附载体树脂液与10～20份机械载体结合，常温固化10～14h、70～100℃干燥10～14h，获得复合载体；其中，机械载体包括铝蜂窝、纸蜂窝、聚甲基丙烯酰亚胺(PMI)泡沫和聚对苯二甲酸乙二醇酯(PET)泡沫中的一种或多种；吸附载体不仅可以包括碳纤维、活性炭和石墨烯的碳基载体，并且还可以包括氧化铝、氧化硅和氧化钛的其它载体；树脂液包括环氧树脂液、聚酰亚胺树脂液和异氰酸酯树脂液中的一种或多种。0.1 to 20 parts of the adsorption carrier is mixed with 0.1 to 20 parts of the resin liquid to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid is combined with 10 to 20 parts of the mechanical carrier by dipping, spraying or coating, and cured at room temperature. 10~14h, 70~100°C drying for 10-14h to obtain a composite carrier; wherein the mechanical carrier comprises aluminum honeycomb, paper honeycomb, polymethacrylimide (PMI) foam and polyethylene terephthalate ( PET) one or more of the foam; the adsorption carrier may include not only a carbon-based carrier of carbon fiber, activated carbon, and graphene, but may also include other carriers of alumina, silica, and titania; the resin solution includes an epoxy resin solution One or more of a polyimide resin liquid and an isocyanate resin liquid.
实施例1Example 1
将5份活性炭与10份环氧树脂液混合，配制成吸附载体树脂液，然后采用喷淋的方式将吸附载体树脂液与10份机械载体铝蜂窝结合，常温固化12h、在烘箱中80℃干燥12h，获得复合载体。5 parts of activated carbon and 10 parts of epoxy resin were mixed to prepare adsorption carrier resin liquid, and then the adsorption carrier resin liquid was sprayed to 10 parts of mechanical carrier aluminum honeycomb, cured at room temperature for 12 hours, dried in an oven at 80 ° C. At 12 h, a composite vector was obtained.
实施例2Example 2
将0.1份碳纤维与0.1份聚酰亚胺树脂液混合，配制成吸附载体树脂液，然后采用浸渍的方式将吸附载体树脂液与10份机械载体纸蜂窝结合，常温固化10h、在烘箱中70℃干燥14h，获得复合载体。0.1 part of carbon fiber is mixed with 0.1 part of polyimide resin liquid to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid is combined with 10 parts of mechanical carrier paper honeycomb by dipping, and cured at room temperature for 10 hours, 70 ° C in an oven. After drying for 14 h, a composite carrier was obtained.
实施例3Example 3
将10份石墨烯、10份活性炭与20份异氰酸酯树脂液混合，配制成吸附 载体树脂液，然后采用涂覆的方式将吸附载体树脂液与20份机械载体PMI泡沫结合，常温固化14h、在烘箱中100℃干燥10h，获得复合载体。10 parts of graphene, 10 parts of activated carbon and 20 parts of isocyanate resin liquid were mixed to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid was combined with 20 parts of mechanical carrier PMI foam by coating, and cured at room temperature for 14 hours in an oven. After drying at 100 ° C for 10 h, a composite carrier was obtained.
实施例4Example 4
将5份碳纤维、5份氧化硅与15份环氧树脂液混合，配制成吸附载体树脂液，然后采用涂覆的方式将吸附载体树脂液与18份机械载体PET泡沫结合，常温固化12h、在烘箱中90℃干燥12h，获得复合载体。5 parts of carbon fiber, 5 parts of silicon oxide and 15 parts of epoxy resin were mixed to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid was combined with 18 parts of mechanical carrier PET foam by coating, and cured at room temperature for 12 hours. The mixture was dried in an oven at 90 ° C for 12 h to obtain a composite carrier.
实施例5Example 5
将3份活性炭、2份氧化钛与8份异氰酸酯树脂液混合，配制成吸附载体树脂液，然后采用浸渍的方式将吸附载体树脂液与10份机械载体PMI泡沫结合，常温固化14h、在烘箱中100℃干燥10h，获得复合载体。3 parts of activated carbon, 2 parts of titanium oxide and 8 parts of isocyanate resin liquid were mixed to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid was combined with 10 parts of mechanical carrier PMI foam by dipping, and cured at room temperature for 14 hours in an oven. Drying at 100 ° C for 10 h gave a composite support.
实施例6Example 6
将7份石墨烯、6份氧化铝与12份聚酰亚胺树脂液混合，配制成吸附载体树脂液，然后采用涂覆的方式将吸附载体树脂液与16份机械载体铝蜂窝结合，常温固化10h、在烘箱中70℃干燥14h，获得复合载体。7 parts of graphene, 6 parts of alumina and 12 parts of polyimide resin liquid are mixed to prepare an adsorption carrier resin liquid, and then the adsorption carrier resin liquid is combined with 16 parts of mechanical carrier aluminum honeycomb by coating, and cured at room temperature. After 10 h, it was dried in an oven at 70 ° C for 14 h to obtain a composite carrier.
采用本领域中常用的方法测试了由实施例1至实施例6中的复合载体制备的催化剂对苯类污染物的去除率和选择性以及该催化剂的再生次数，测试结果见下表1：The removal rate and selectivity of the benzene-based contaminants and the number of regenerations of the catalysts prepared by the composite carriers of Examples 1 to 6 were tested by methods commonly used in the art, and the test results are shown in Table 1 below:
表1Table 1
  污染物Contaminant 吸附载体Adsorption carrier 去除率Removal rate 选择性Selectivity 再生次数Number of regenerations
实施例1Example 1 苯benzene 活性炭Activated carbon 85％85% 86％86% 4242
实施例2Example 2 甲苯Toluene 碳纤维carbon fiber 87％87% 84％84% 4040
实施例3Example 3 苯benzene 石墨烯和活性炭Graphene and activated carbon 90％90% 87％87% 4343
实施例4Example 4 间二甲苯Meta-xylene 碳纤维和氧化硅Carbon fiber and silicon oxide 89％89% 90％90% 3939
实施例5Example 5 甲苯Toluene 活性炭和氧化钛Activated carbon and titanium oxide 92％92% 91％91% 4040
实施例6Example 6 间二甲苯Meta-xylene 石墨烯和氧化铝Graphene and alumina 90％90% 85％85% 4141
由表1可见，本发明通过在复合载体中引入碳基载体，使得制备成的催化剂可以实现对苯类污染物的选择性去除，使得制备的催化剂去除率高达92％，选择性高达91％，实现了对苯类污染物的选择性高效去除；此外， 通过机械载体与高比表面积的吸附载体的结合使用，在保证气态污染物通过催化剂时流通顺畅的同时保证了催化剂不易流失，使得催化剂的再生次数高达43次，提高了催化剂的使用寿命，有效克服催化剂在长期使用过程中的磨损、流失及难回收的问题。由本发明的复合载体制备的催化剂可应用于空气净化器、空调、防毒面具以及换气扇等，可有效改善产品对苯类污染物的去除效果，降低对环境和人体的污染性和危害性，并且可长期使用。It can be seen from Table 1 that the present invention can realize the selective removal of benzene pollutants by introducing a carbon-based carrier into the composite carrier, so that the prepared catalyst removal rate is as high as 92% and the selectivity is as high as 91%. The selective and efficient removal of benzene pollutants is realized; in addition, the combination of the mechanical carrier and the high specific surface area adsorption carrier ensures smooth circulation of the gaseous pollutants while passing through the catalyst, and ensures that the catalyst is not easily lost, so that the catalyst is The number of regenerations is up to 43 times, which improves the service life of the catalyst and effectively overcomes the problems of wear, loss and difficult recovery of the catalyst during long-term use. The catalyst prepared by the composite carrier of the invention can be applied to an air purifier, an air conditioner, a gas mask, a ventilation fan, etc., which can effectively improve the removal effect of the product on the benzene pollutants, reduce the pollution and harm to the environment and the human body, and can long-term use.
本领域技术人员应理解，以上实施例仅是示例性实施例，在不背离本发明的精神和范围的情况下，可以进行多种变化、替换以及改变。Those skilled in the art will appreciate that the above-described embodiments are merely exemplary embodiments, and various changes, substitutions and changes may be made without departing from the spirit and scope of the invention.

Claims (13)

  1. 一种复合载体，其特征在于，包括：A composite carrier, comprising:
    机械载体；Mechanical carrier
    吸附载体；以及Adsorption carrier;
    树脂液，Resin solution,
    其中，所述机械载体、所述吸附载体和所述树脂液的质量比为10～20:0.1～20:0.1～20。The mass ratio of the mechanical carrier, the adsorption carrier and the resin liquid is 10-20:0.1-20:0.1-20.
  2. 根据权利要求1所述复合载体，其特征在于，所述机械载体包括铝蜂窝、纸蜂窝、聚甲基丙烯酰亚胺泡沫和聚对苯二甲酸乙二醇酯泡沫中的一种或多种。The composite carrier according to claim 1, wherein the mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam. .
  3. 根据权利要求1所述复合载体，其特征在于，所述吸附载体包括碳基载体；所述碳基载体包括碳纤维、活性炭和石墨烯中的一种或多种。The composite carrier according to claim 1, wherein said adsorption carrier comprises a carbon-based support; and said carbon-based support comprises one or more of carbon fibers, activated carbon and graphene.
  4. 根据权利要求3所述复合载体，其特征在于，所述吸附载体还包括其它载体；所述其它载体包括氧化铝、氧化硅和氧化钛中的一种或多种。The composite carrier according to claim 3, wherein said adsorption carrier further comprises other carriers; said other carrier comprising one or more of alumina, silica and titania.
  5. 根据权利要求1所述复合载体，其特征在于，所述树脂液包括环氧树脂液、聚酰亚胺树脂液和异氰酸酯树脂液中的一种或多种。The composite carrier according to claim 1, wherein the resin liquid comprises one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
  6. 一种制备复合载体的方法，其特征在于，包括以下步骤：A method of preparing a composite carrier, comprising the steps of:
    将吸附载体与树脂液混合，配置成吸附载体树脂液；Mixing the adsorption carrier with the resin liquid, and arranging to adsorb the carrier resin liquid;
    将所述吸附载体树脂液与机械载体结合；以及Combining the adsorbent carrier resin liquid with a mechanical carrier;
    固化、干燥，得到所述复合载体。Curing and drying to obtain the composite carrier.
  7. 根据权利要求6所述的方法，其特征在于，所述机械载体、所述吸附载体和所述树脂液的质量比为10～20:0.1～20:0.1～20。The method according to claim 6, wherein the mechanical carrier, the adsorption carrier and the resin liquid have a mass ratio of 10 to 20: 0.1 to 20: 0.1 to 20.
  8. 根据权利要求6所述的方法，其特征在于，通过浸渍、喷淋或涂覆的方式将所述吸附载体树脂液与所述机械载体结合。The method according to claim 6, wherein the adsorption carrier resin liquid is combined with the mechanical carrier by dipping, spraying or coating.
  9. 根据权利要求6所述的方法，其特征在于，所述机械载体包括铝蜂窝、纸蜂窝、聚甲基丙烯酰亚胺泡沫和聚对苯二甲酸乙二醇酯泡沫中的一种或多种。The method of claim 6 wherein said mechanical carrier comprises one or more of an aluminum honeycomb, a paper honeycomb, a polymethacrylimide foam, and a polyethylene terephthalate foam. .
  10. 根据权利要求6所述的方法，其特征在于，所述吸附载体包括碳基载体；所述碳基载体包括碳纤维、活性炭和石墨烯中的一种或多种；The method according to claim 6, wherein said adsorption carrier comprises a carbon-based support; said carbon-based support comprises one or more of carbon fibers, activated carbon and graphene;
  11. 根据权利要求10所述的方法，其特征在于，所述吸附载体还包括其它载体；所述其它载体包括氧化铝、氧化硅和氧化钛中的一种或多种。The method of claim 10 wherein said adsorptive support further comprises other supports; said other support comprising one or more of alumina, silica and titania.
  12. 根据权利要求6所述的方法，其特征在于，所述树脂液包括环氧树脂液、聚酰亚胺树脂液和异氰酸酯树脂液中的一种或多种。The method according to claim 6, wherein the resin liquid comprises one or more of an epoxy resin liquid, a polyimide resin liquid, and an isocyanate resin liquid.
  13. 根据权利要求1-5中任一项所述的复合载体在催化剂中的应用。Use of a composite support according to any one of claims 1 to 5 in a catalyst.
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