CN1490079A - High-adsorbability glass beads with photocatalysis function - Google Patents
High-adsorbability glass beads with photocatalysis function Download PDFInfo
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- CN1490079A CN1490079A CNA031253598A CN03125359A CN1490079A CN 1490079 A CN1490079 A CN 1490079A CN A031253598 A CNA031253598 A CN A031253598A CN 03125359 A CN03125359 A CN 03125359A CN 1490079 A CN1490079 A CN 1490079A
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Abstract
A photocatalytic glass microbead with high adsorbability is composed of hollow glass microbead as carrier and surficial photocatalyst film consisting of nano-class activated carbon and Ag, Zn or Cu modified TiO2. It is prepared through adding gelatinized starch, butyl titanate, diethanol amine, polyethanediol and silver (or Copper or Zinc) nitrate to absolute alcohol, stirring to obtain sol, immersing the clean hollow glass microbeads in it, and carbonizing and activating in protecting atmosphere at 300-650 deg.C. It can be used to clean water.
Description
Technical field
The present invention relates to surface, generated in-situ nano active charcoal of load and nano-TiO at a kind of hollow glass bead
2The material of photochemical catalyst laminated film is adsorptivity and the better TiO that possesses active carbon
2The glass microballoon of photocatalysis efficiency.
Background technology
The river pollution thing is very complicated, and particularly when containing relatively large organic oil pollutant and swim in the water surface, pollutant can be stopped contacting of water body and atmosphere, influences the existence of water body animal and plant.Simultaneously the grease pollutant swims in the water surface, administers their comparatively difficulties, particularly has under the situation more refractory reason at water surface with the oil film thin layer.Phase late 1990s, develop the float type photochemical catalyst both at home and abroad in succession and cut the body material, marine pollution is administered.The existing in this regard research of Japan-US and more European countries.But, TiO
2Photochemical catalyst loads on the hollow glass micropearl surface, only the organic matter that can be adsorbed on bead surface is carried out photocatalysis, and then photocatalysis efficiency is relatively poor for other organic pollutions in the water.Main cause is exactly TiO
2Photocatalyst surface is to organic fine particles, organic lipid, and tiny organism adsorption capacity is poor, thereby influences photocatalysis efficiency.Photocatalysis is a kind of comparatively cleaning, the depollution of environment technology of energy savings.Because the operating efficiency of photocatalysis technology self is slower, so various countries competitively strengthen the research to photocatalysis efficiency, as improving function vector, increase the compound combination property of catalysis material, improve the nanometer particle size of catalysis material, improve photocatalysis performance with this.Add the metal dissolved salt and modify, improve the efficient of photochemical catalyst.
Introduce in the Chinese patent application number 02139274.9,02139299.4,02147715.9, at glass microballoon or fiberglass surfacing load composite Nano active carbon and photocatalyst film, requirement is at surfaces of carrier materials load transition zone, add micro activated carbon particle simultaneously, its technology is more numerous and diverse, cost is high.
Summary of the invention
The objective of the invention is to adopt the compound new technology of material, study a kind of glass microballoon with the high photochemical catalyst performance of high absorption property, need not prepare transition zone and add micro activated carbon particle, this glass microballoon is used for the marine pollution light catalytic purifying, preparation technology is simple, and cost is low.
Reach the photocatalysis glass microballoon of the object of the invention; composite photocatalyst thin-film by the honeycomb hole structure of hollow glass micropearl carrier and its top layer load is formed; described composite photocatalyst thin-film by generated in-situ active carbon with form through the titanium dioxide optical catalyst of silver or zinc or copper modified metal oxide; described generated in-situ active carbon is to be joined in the colloidal sol of impregnated carrier by gelatinized starch; charing at high temperature in nitrogen and argon-mixed protective atmosphere; steam activation and the active carbon that generates; its amounts of activated carbon is 3～30% of a photocatalysis film weight, 70～97% of titanium dioxide optical catalyst amount film weight.Its film thickness is not particularly limited, and is generally 0.05 μ～20 μ.
Described protection gas is the gaseous mixture of 20～30% nitrogen and 80～70% argons.
Gelatinized starch charing and activation temperature are 300 ℃～650 ℃.
Described titanium dioxide optical catalyst through silver or zinc or copper modified metal oxide is TiO
2Presoma metatitanic acid fourth fat joins in the colloidal sol of impregnated carrier, in protective atmosphere, generates when high-temperature process is soaked with the carrier of colloidal sol.
Described hollow glass micropearl be by flue dust through pickling, pure washing, soak with NaOH 10～50% solution again, wash, in≤80 ℃ of oven dry and nano-glass hollow beads of making down.
Described colloidal sol is by absolute ethyl alcohol and adds butyl titanate, silver nitrate or the zinc nitrate of required weight or the solution composition of copper nitrate, diethanol amine, polyethylene glycol and the abundant stirring and evenly mixing of gelatinized starch.
Described colloidal sol is the butyl titanate by absolute ethyl alcohol and absolute ethyl alcohol weight 3～40%, after adding 0.1～2% silver nitrate of butyl titanate weight or zinc nitrate or copper nitrate and stirring, add homogeneous mixture weight 0.1～5% diethanol amine again, 0.1 after～10% polyethylene glycol stirred, the gelatinized starch that adds its mixture weight 1～50% is sufficient to be stirred and forms.
Described hollow glass micropearl is the pearl that floats of adopting the interior part formation of flue dust, removes broken body and selected hollow float bead.
Photocatalysis hollow glass micropearl step of preparation process of the present invention is as follows:
1, will immerse red fuming nitric acid (RFNA) liquid 1～3 hour through the clean microballon of water rinse, and get the liquid level microballon and wash neutrality, and add sodium hydroxide solution and soaked 1～3 hour, and get the liquid level microballon and be washed to neutrality, in 80 ℃ of dry for standby;
2, get soluble starch, add in the entry by common known manner gelatinization, producing its water content is 30%～80%, and hot dextrin is preserved standby.
3, get absolute ethyl alcohol, add the butyl titanate of absolute ethyl alcohol weight 3～40%, metatitanic acid fourth fat consumption adds 0.1
The silver nitrate of %～2% weight ratio or zinc nitrate or copper nitrate stirred 0.5～2 hour altogether, the diethanol amine that adds weight ratio 0.1%～5%, 0.1%～10% polyethylene glycol stirred 1～2 hour altogether, and the gelatinized starch that slowly adds weight ratio 1%～50% stirs and became colloidal sol in 0.5～2 hour.
4, by weight 1: 1 with treated microballon and colloidal sol blend, soak into and be placed on 80 ℃～140 ℃ oven dry in baking oven inherence.
5, the microballon that takes out oven dry repeats to add colloidal sol blend drying (taking out the oven dry sample must disperse through writing brush) 2～5 times.
6, the bead surface of mixing, oven dry, dispersion generally is impregnated with 1～5 layer photocatalyst sol; this sample of dry for standby is placed in the high-temperature gas protection stove; charge into 20%～30% nitrogen, 80%～70% argon gas; go in the stove through the mixing bottle; slowly be warmed up to 300 ℃～400 ℃, be incubated 1～2 hour, charge into through 300 ℃～650 ℃ in washing, the higher blend gas of water content; be incubated 1～2 hour, cool off standby.
Diethanol amine that adds in the colloidal sol among the present invention and poly-diethanol are volatilized when high-temperature process is impregnated with the glass microballoon of colloidal sol, and the composite photocatalyst thin-film ectonexine that colloidal sol is formed forms cellular hole, has increased the active surface of photocatalysis glass microballoon.
The specific embodiment
One, get and float pearl and add red fuming nitric acid (RFNA) and soaked 3 hours, get the surface and float pearl and go into pure water and be washed till neutrality, add sodium oxide molybdena 20% solution, submergence 2 hours is got the top layer microballon and is added the pure neutrality of washing, 80 ℃ of oven dry in baking oven.
Two, it is altogether molten to get the soluble starch adding distil water, and it is standby fully to add the thermal agitation gelatinization in 20: 100 ratios of starch and water.
Three, get absolute ethyl alcohol 200ml and make cosolvent, add metatitanic acid fourth fat 30ml, silver nitrate 0.2 gram, diethanol amine 2 grams, polyethylene glycol 3 grams stirred 1 hour altogether.
Four, with step 2 gelatinization starch preparation completely, join in the liquid of step 3, its addition is pressed the prepared gelatinized starch amount of former dried starch of metatitanic acid fourth fat weight 10%, stirs that to make colloidal sol in 1 hour standby.
Five, 1 gained glass microballoon and 1: 1 volume ratio of colloidal sol are soaked blend set by step, place baking oven in 80～120 ℃ of dryings, take out with writing brush and disperse, and heavily add colloidal sol and mix the back drying, so repeat four times.
Six, dried microballon places the gas shield stove; with feeding nitrogen 30%; argon gas 70%, hybrid protection gas are warmed up to 400 ℃, are incubated 2 hours; add steam and be warmed up to 550 ℃; be incubated 2 hours, the steam of cutting off the water is lowered the temperature with stove; protection gas does not stop, and the cooling back is taken out microballon and promptly obtained the synthetic photocatalysis glass microballoon with nano active charcoal and photocatalyst film layer of original position.
Claims (6)
1; a kind of photocatalysis glass microballoon; it is characterized in that forming by the composite photocatalyst thin-film of the honeycomb hole structure of hollow glass micropearl carrier and its top layer load; described composite photocatalyst thin-film; by generated in-situ nano active charcoal with form through the titanium dioxide optical catalyst of silver or zinc or copper modified metal oxide; described generated in-situ active carbon; be to join in the colloidal sol of impregnated carrier by gelatinized starch; charing at high temperature in the argon-mixed protective atmosphere of nitrogen; steam activation and the active carbon that generates; its amounts of activated carbon is 3～30% of a photocatalysis film weight, and the titanium dioxide optical catalyst amount is 97～70% of a photocatalysis film weight.
2, photocatalysis glass microballoon as claimed in claim 1 is characterized in that described protection gas is the gaseous mixture of 20～30% nitrogen and 80～70% argons.
3, photocatalysis glass microballoon as claimed in claim 1 is characterized in that described gelatinized starch charing and activation temperature are 300 ℃～650 ℃.
4, photocatalysis glass microballoon as claimed in claim 1, it is characterized in that described hollow glass micropearl is through pickling, pure washing by flue dust, soak with NaOH 10～50% solution again, after washing, in≤80 ℃ of nano-glass hollow beads of drying down and making.
5, photocatalysis glass microballoon as claimed in claim 1, it is characterized in that described colloidal sol is butyl titanate, silver nitrate or zinc nitrate or copper nitrate, diethanol amine, polyethylene glycol and the gelatinized starch by absolute ethyl alcohol and the required weight of adding, the fully solution of stirring and evenly mixing.
6, photocatalysis glass microballoon as claimed in claim 1, it is characterized in that described colloidal sol is the butyl titanate by absolute ethyl alcohol and absolute ethyl alcohol weight 3～40%, after adding butyl titanate weight 0.1～2% silver nitrate or zinc nitrate or copper nitrate and stirring, add homogeneous mixture weight 0.1～5% diethanol amine again, 0.1 after～10% polyethylene glycol stirred, the gelatinized starch that adds its mixture weight 1～50% is sufficient to be stirred and forms.
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| CN 03125359 CN1210102C (en) | 2003-09-01 | 2003-09-01 | High-adsorbability glass beads with photocatalysis function |
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| CN 03125359 CN1210102C (en) | 2003-09-01 | 2003-09-01 | High-adsorbability glass beads with photocatalysis function |
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| CN1490079A true CN1490079A (en) | 2004-04-21 |
| CN1210102C CN1210102C (en) | 2005-07-13 |
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| CN1317069C (en) * | 2005-01-07 | 2007-05-23 | 武汉理工大学 | Prepn process of multilayer porous active compound TiO2 photocatalyst |
| CN100366584C (en) * | 2005-07-05 | 2008-02-06 | 南京大学 | Preparation method of TiO2 photocatalyst for loading on ceramic surface |
| CN101857390A (en) * | 2009-04-10 | 2010-10-13 | 中国科学院福建物质结构研究所 | Composite powder with antibacterial and heat insulation functions and preparation method and purposes thereof |
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN101760171B (en) * | 2008-12-25 | 2013-08-14 | 西北工业大学 | Optical resonance composite material in noble metal/titanium dioxide micro-nano structure |
| CN105126872A (en) * | 2015-08-19 | 2015-12-09 | 黑龙江大学 | Preparation method and application of visible-light responsible chromium-sulfur codoped TiO2/hollow glass bead composite catalyst |
| CN105797691A (en) * | 2016-03-30 | 2016-07-27 | 河南工业大学 | Porous particle floating activated carbon composite and preparation method thereof |
| CN105833841A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of activated carbon-based adsorption material |
| CN106268947A (en) * | 2016-07-20 | 2017-01-04 | 上海航天设备制造总厂 | A kind of preparation method of nanometer starch crystal load gold nano grain effective catalyst |
| CN108435168A (en) * | 2018-04-23 | 2018-08-24 | 齐鲁工业大学 | One kind having visible absorption and efficient CO2The composite photo-catalyst and preparation method thereof of absorption and conversion performance |
| CN108607616A (en) * | 2016-12-09 | 2018-10-02 | 北京有色金属研究总院 | A kind of nonmetallic and graphene oxide codope lightweight catalysis material preparation process |
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| CN108863092A (en) * | 2018-08-30 | 2018-11-23 | 浙江省交通运输科学研究院 | A kind of glass microballoon and preparation method thereof of self assembly surface layer microcellular structure |
| CN109052465A (en) * | 2018-08-30 | 2018-12-21 | 浙江省交通运输科学研究院 | A kind of glass microballoon-nanometer titanium dioxide compound and preparation process |
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| CN1317069C (en) * | 2005-01-07 | 2007-05-23 | 武汉理工大学 | Prepn process of multilayer porous active compound TiO2 photocatalyst |
| CN100366584C (en) * | 2005-07-05 | 2008-02-06 | 南京大学 | Preparation method of TiO2 photocatalyst for loading on ceramic surface |
| CN101760171B (en) * | 2008-12-25 | 2013-08-14 | 西北工业大学 | Optical resonance composite material in noble metal/titanium dioxide micro-nano structure |
| CN101857390A (en) * | 2009-04-10 | 2010-10-13 | 中国科学院福建物质结构研究所 | Composite powder with antibacterial and heat insulation functions and preparation method and purposes thereof |
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN103007931B (en) * | 2012-11-22 | 2014-05-21 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN105126872A (en) * | 2015-08-19 | 2015-12-09 | 黑龙江大学 | Preparation method and application of visible-light responsible chromium-sulfur codoped TiO2/hollow glass bead composite catalyst |
| US11707727B2 (en) | 2016-02-23 | 2023-07-25 | Sony Corporation | Solidified porous carbon material and method of manufacturing the same |
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| CN105797691B (en) * | 2016-03-30 | 2019-03-08 | 河南工业大学 | A kind of porous prilled floatability absorbent charcoal composite material and preparation method thereof |
| CN105797691A (en) * | 2016-03-30 | 2016-07-27 | 河南工业大学 | Porous particle floating activated carbon composite and preparation method thereof |
| CN105833841A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of activated carbon-based adsorption material |
| CN106268947A (en) * | 2016-07-20 | 2017-01-04 | 上海航天设备制造总厂 | A kind of preparation method of nanometer starch crystal load gold nano grain effective catalyst |
| CN108607616A (en) * | 2016-12-09 | 2018-10-02 | 北京有色金属研究总院 | A kind of nonmetallic and graphene oxide codope lightweight catalysis material preparation process |
| CN108435168A (en) * | 2018-04-23 | 2018-08-24 | 齐鲁工业大学 | One kind having visible absorption and efficient CO2The composite photo-catalyst and preparation method thereof of absorption and conversion performance |
| CN108435168B (en) * | 2018-04-23 | 2021-04-13 | 齐鲁工业大学 | Visible light absorption and high-efficiency CO2Composite photocatalyst with adsorption and conversion performance and preparation method thereof |
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| CN108863092A (en) * | 2018-08-30 | 2018-11-23 | 浙江省交通运输科学研究院 | A kind of glass microballoon and preparation method thereof of self assembly surface layer microcellular structure |
| CN109052465A (en) * | 2018-08-30 | 2018-12-21 | 浙江省交通运输科学研究院 | A kind of glass microballoon-nanometer titanium dioxide compound and preparation process |
| CN109052465B (en) * | 2018-08-30 | 2020-11-13 | 浙江省交通运输科学研究院 | Glass bead-nano titanium dioxide compound and preparation process thereof |
| CN112691643A (en) * | 2020-12-23 | 2021-04-23 | 中北大学 | Preparation method of micron spherical activated carbon |
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