CN106750498A - The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam - Google Patents

The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam Download PDF

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Publication number
CN106750498A
CN106750498A CN201611015176.XA CN201611015176A CN106750498A CN 106750498 A CN106750498 A CN 106750498A CN 201611015176 A CN201611015176 A CN 201611015176A CN 106750498 A CN106750498 A CN 106750498A
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preparation
oxidation process
tio
formaldehyde
process function
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王耀斌
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Shaanxi Shengmai Petroleum Co Ltd
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Shaanxi Shengmai Petroleum Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The present invention relates to a kind of preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam.The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam, comprises the following steps：（1）The preparation of polyurethane foam charcoal；（2）The preparation of formaldehyde degradation by photocatalytic oxidation process function Carbon foam.The polyurethane foam charcoal of preparation is presented flourishing network structure, and polyurethane is tightly combined with activated carbon.Support TiO2It is mainly distributed on Carbon foam channel surfaces.TiO2The removal for supporting function Carbon foam PARA FORMALDEHYDE PRILLS(91,95) shows as the synergy of absorption and photocatalytic degradation, the abundant foam-like pore passage structure substantial amounts of attachment point for formaldehyde gas is provided, under the irradiation of ultraviolet light, TiO2It is small molecule, activated carbon addition high and TiO by its photocatalytic degradation2Doping is conducive to the removal of formaldehyde gas.When activated carbon addition is 35%, TiO2When doping is 2%, photocatalytic activity highest reaches 85.3%.

Description

The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam
Technical field
The present invention relates to a kind of preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam.
Background technology
Formaldehyde is a kind of with very supervirulent gas, the construction material of interior decoration, hard board, furniture, coating, oil Paint, textile etc., can discharge formaldehyde, and acquisition time most long up to the more than ten years in use.Work as indoor formaldehyde content It is 0.1 mg/m3When just have peculiar smell and a sense of discomfort, suck high-concentration formaldehyde, respiratory tract and bronchial disease can be caused；Connect for a long time Tactile low dosage formaldehyde can cause slow poisoning, and severe patient causes death.Therefore, the method for exploring effectively removal indoor formaldehyde is mesh One of preceding study hotspot.
Numerous studies have been carried out in terms of formaldehyde removal both at home and abroad.In numerous purification techniques, absorption method and TiO2Light is urged Change method is presently the most widely used Formaldehyde Pollution of Indoor Air purification method.Compared with other adsorbents, activated carbon surface has many Pore structure and various active groups, with adsorption capacity is big, the rate of adsorption fast, the characteristics of be easy to regeneration, in controlling for gaseous formaldehyde Reason aspect is demonstrated by obvious advantage.Charcoal absorption formaldehyde relies primarily on the physics of the micropore and mesoporous PARA FORMALDEHYDE PRILLS(91,95) in its structure Suction-operated, with the extension of use time, the absorption of activated carbon PARA FORMALDEHYDE PRILLS(91,95) gas will reach saturation, lose absorption property.
TiO2The photochemical reaction that the Photo-induced electron transfer process of particle interface is induced is organic in elimination environment Polluter, with remarkable result, it is expected to develop into directly using oxygen in air and solar energy degraded hazardous contaminant Green oxidation technology.By TiO2Show that, used as adsorption site, its strong absorption property can be right for porous charcoal with the compound research of porous charcoal Light concentration organic pollutant be effectively enriched with, concentrated, and is TiO2High concentration reaction environment is provided, accelerates TiO2Photocatalysis drop Solution speed；TiO2The concentration difference of adsorbate inside and outside porous charcoal can be formed as degraded center, the in-situ regeneration of porous charcoal is realized, prolonged Porous charcoal long reaches the time of adsorption saturation, increases the equilibrium adsorption capacity of porous charcoal.In addition, the absorption of porous charcoal is effectively reduced The release of volatility photocatalysis intermediate product, can eliminate the secondary pollution produced by volatile intermediate products.
But conventional carbon not easy-formation, and dust pollution is easily caused, thus be accordingly used in the function of synthesis indoor VOCs purification Carbon Materials remain certain defect.
The content of the invention
The present invention is directed to propose a kind of preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam.
Technical program of the present invention lies in：
The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam, comprises the following steps：
（1）The preparation of polyurethane foam charcoal
By ACrawAdd glass mold in, plus people's polyethers, the silicone oil that hard bubbles, water, pentamethyl-diethylenetriamine, dichloro one fluoroethane, Ethylenimine is well mixed in a mold, and 1 min is stirred with the speed of 500~600 r/min, adds the isocyanide of diphenyl methane two Acid esters, its free foaming is made with the speed strong stirring 45S of 1000 r/min, and 24 h are cured at room temperature, is subsequently placed in Muffle furnace In with 5 DEG C/min be warmed up to 350 DEG C charing l h, be made polyurethane foam charcoal；
（2）The preparation of formaldehyde degradation by photocatalytic oxidation process function Carbon foam
Prepare 50 mL, the TiO of mass fraction 1%2Solution, ultrasonic 15 min makes its uniform mixing under weak ultrasonic wave；Will system The polyurethane foam charcoal got ready is added to 50 mL, the TiO of mass fraction 1%2In solution, taken out in 100 after 15 min of dipping DEG C drying 24 h, obtain formaldehyde degradation by photocatalytic oxidation process function Carbon foam.
Described m（Polyethers）：m（Methyl diphenylene diisocyanate）It is 10：9.
The technical effects of the invention are that：
The present invention is the thermally treated prepared polyurethane foam charcoal of raw material with polyurethane and activated carbon, then supports TiO2Being obtained has The function Carbon foam of photocatalytic activity.The polyurethane foam charcoal of preparation is presented flourishing network structure, polyurethane and activated carbon knot Close tight.Support TiO2It is mainly distributed on Carbon foam channel surfaces.TiO2The removal for supporting function Carbon foam PARA FORMALDEHYDE PRILLS(91,95) shows as inhaling Echo the synergy of photocatalytic degradation, the abundant foam-like pore passage structure substantial amounts of attachment point for formaldehyde gas is provided, in purple Under the irradiation of outer light, TiO2It is small molecule, activated carbon addition high and TiO by its photocatalytic degradation2Doping is conducive to first The removal of aldehyde gas.When activated carbon addition is 35%, TiO2When doping is 2%, photocatalytic activity highest reaches 85.3%.
Specific embodiment
The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam, comprises the following steps：
（1）The preparation of polyurethane foam charcoal
By ACrawAdd glass mold in, plus people's polyethers, the silicone oil that hard bubbles, water, pentamethyl-diethylenetriamine, dichloro one fluoroethane, Ethylenimine is well mixed in a mold, and 1 min is stirred with the speed of 500~600 r/min, adds the isocyanide of diphenyl methane two Acid esters, its free foaming is made with the speed strong stirring 45S of 1000 r/min, and 24 h are cured at room temperature, is subsequently placed in Muffle furnace In with 5 DEG C/min be warmed up to 350 DEG C charing l h, be made polyurethane foam charcoal；
（2）The preparation of formaldehyde degradation by photocatalytic oxidation process function Carbon foam
Prepare 50 mL, the TiO of mass fraction 1%2Solution, ultrasonic 15 min makes its uniform mixing under weak ultrasonic wave；Will system The polyurethane foam charcoal got ready is added to 50 mL, the TiO of mass fraction 1%2In solution, taken out in 100 after 15 min of dipping DEG C drying 24 h, obtain formaldehyde degradation by photocatalytic oxidation process function Carbon foam.
Wherein, described m（Polyethers）：m（Methyl diphenylene diisocyanate）It is 10：9.

Claims (2)

1. the preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam, it is characterised in that：Comprise the following steps：
（1）The preparation of polyurethane foam charcoal
By ACrawAdd glass mold in, plus people's polyethers, the silicone oil that hard bubbles, water, pentamethyl-diethylenetriamine, dichloro one fluoroethane, Ethylenimine is well mixed in a mold, and 1 min is stirred with the speed of 500~600 r/min, adds the isocyanide of diphenyl methane two Acid esters, its free foaming is made with the speed strong stirring 45S of 1000 r/min, and 24 h are cured at room temperature, is subsequently placed in Muffle furnace In with 5 DEG C/min be warmed up to 350 DEG C charing l h, be made polyurethane foam charcoal；
（2）The preparation of formaldehyde degradation by photocatalytic oxidation process function Carbon foam
Prepare 50 mL, the TiO of mass fraction 1%2Solution, ultrasonic 15 min makes its uniform mixing under weak ultrasonic wave；To prepare Good polyurethane foam charcoal is added to 50 mL, the TiO of mass fraction 1%2In solution, taken out in 100 DEG C after 15 min of dipping 24 h are dried, formaldehyde degradation by photocatalytic oxidation process function Carbon foam is obtained.
2. the preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam according to claim 1, it is characterised in that：Described m（Polyethers）：m（Methyl diphenylene diisocyanate）It is 10：9.
CN201611015176.XA 2016-11-18 2016-11-18 The preparation method of formaldehyde degradation by photocatalytic oxidation process function Carbon foam Pending CN106750498A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163551A (en) * 2017-06-09 2017-09-15 合肥嘉仕诚能源科技有限公司 A kind of nano material with air purification function and preparation method thereof
CN107189404A (en) * 2017-06-09 2017-09-22 合肥嘉仕诚能源科技有限公司 A kind of nano material with function of absorbing formaldehyde and preparation method thereof
CN110407999A (en) * 2019-07-29 2019-11-05 江苏绿源新材料有限公司 Utilize the active carbon foams and preparation method of the active carbon preparation that exhaust gas is absorbed during polyurethane foam
CN110538642A (en) * 2019-08-20 2019-12-06 焦作大学 Composite material for adsorbing formaldehyde and preparation method thereof
CN110665481A (en) * 2019-09-29 2020-01-10 焦作大学 Composite material for indoor gas purification, preparation method thereof and wallpaper
CN111138630A (en) * 2020-01-08 2020-05-12 万华化学集团股份有限公司 Composition for preparing polyurethane wood-like material
CN113680317A (en) * 2021-08-26 2021-11-23 中国矿业大学 Titanium dioxide/coal-based hierarchical pore film foam carbon composite material and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163551A (en) * 2017-06-09 2017-09-15 合肥嘉仕诚能源科技有限公司 A kind of nano material with air purification function and preparation method thereof
CN107189404A (en) * 2017-06-09 2017-09-22 合肥嘉仕诚能源科技有限公司 A kind of nano material with function of absorbing formaldehyde and preparation method thereof
CN110407999A (en) * 2019-07-29 2019-11-05 江苏绿源新材料有限公司 Utilize the active carbon foams and preparation method of the active carbon preparation that exhaust gas is absorbed during polyurethane foam
CN110538642A (en) * 2019-08-20 2019-12-06 焦作大学 Composite material for adsorbing formaldehyde and preparation method thereof
CN110538642B (en) * 2019-08-20 2022-08-23 焦作大学 Composite material for adsorbing formaldehyde and preparation method thereof
CN110665481A (en) * 2019-09-29 2020-01-10 焦作大学 Composite material for indoor gas purification, preparation method thereof and wallpaper
CN110665481B (en) * 2019-09-29 2022-08-26 焦作大学 Composite material for indoor gas purification, preparation method thereof and wallpaper
CN111138630A (en) * 2020-01-08 2020-05-12 万华化学集团股份有限公司 Composition for preparing polyurethane wood-like material
CN113680317A (en) * 2021-08-26 2021-11-23 中国矿业大学 Titanium dioxide/coal-based hierarchical pore film foam carbon composite material and preparation method thereof

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Application publication date: 20170531