CN1524611A - Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof - Google Patents
Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof Download PDFInfo
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- CN1524611A CN1524611A CNA031254284A CN03125428A CN1524611A CN 1524611 A CN1524611 A CN 1524611A CN A031254284 A CNA031254284 A CN A031254284A CN 03125428 A CN03125428 A CN 03125428A CN 1524611 A CN1524611 A CN 1524611A
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- photochemical catalyst
- phenolic resin
- activated carbon
- based activated
- carbon composite
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Abstract
The invention relates to a composite of decomposing organic phenol- containing waste water, namely a photocatalyst-Arcolitebased active carbon composite, as well as its preparing method. Its character: Arcolite 40-100 shares; photocatalyst 10-50 shares; active agent 20-100 shares. Its preparing method: (1) batching; (2) carbonizing: proportionally mixing powdery Arcolite and photocatalyst powder to finely mill, screening by 200-eye sieve, and then carbonizing into powdery carbon after 1-4 hours under the protection of nitrogen gas; (3) activating: fully mixing the powdery carbon with the active agent in the weight proportion to activate for 2-4 hours under the protection of nitrogen gas, cooling the product to fully wash by water to eliminate alkali component, and then drying to obtain the finished product. Under the action of ultraviolet ray, it can make high-efficiency decomposition on organic and harmful matters of organic phenol; its production process is simple and its production cost is low.
Description
Technical field
The present invention relates to composite of the organic phenol wastewater of a kind of resolution process and preparation method thereof, photochemical catalyst-phenolic resin-based activated carbon composite and preparation method thereof particularly, be applicable to that resolution process phenol wastewater and other contain organic poisonous waste water and (as contain benzene organic wastewater, contain organic agricultural chemicals waste water, contain organic sulfur class waste water etc.).
Background technology
Scientific research confirms, contain harmful substances such as a large amount of carcinogenic, environmental hormones in the phenol waste water, and it is wider to originate, to human lives and environment structure serious threat, it is one of object of countries in the world emphasis monitoring and improvement, the phenol content that China's strict regulations enter in the sewage of municipal sewage system can not surpass 1.0mg/L, at present domestic and international improvement method, active carbon adsorption is roughly arranged, biological degradation method, and photocatalyst for degrading method, it is big that above method ubiquity the oxidant consumption amount, processing time is long, shortcomings such as cost height.In recent years Japan has developed in succession the photochemical catalyst inorganic gel has been coated in active carbon, porous ceramics, the surface of porous metals, (spy opens 2001-232206 to make porous matter optic catalytic composite material, Te Kaiping 8-196903), utilize the collection organic toxic substance of porous matrix, help improving the efficient that photochemical catalyst decomposes organic toxic substance, but because photochemical catalyst only is applied to the porous mass surface, can not enter porous inside, the efficient that has influence on photochemical catalyst decomposition organic toxic further improves, owing to the coating of photochemical catalyst, reduced the surface area of porous mass simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of photochemical catalyst-phenolic resin-based activated carbon composite that helps the organic phenol wastewater of resolution process and preparation method thereof.By composite means photochemical catalyst is assembled on the phenolic resin-based activated carbon, make photochemical catalyst can touch organic phenol, the noxious material that is adsorbed on the phenolic resin-based activated carbon to greatest extent, under action of ultraviolet ray, the organic phenol of high efficiency decomposition is organic, noxious material etc.
To achieve these goals, technical scheme of the present invention is: photochemical catalyst-phenolic resin-based activated carbon composite is characterized in that: it comprises phenolic resins, photochemical catalyst, activating agent, and the weight proportion of each constituent is: phenolic resins 40-100 part; Photochemical catalyst 10-50 part; Activating agent 20-100 part.
The phenolic resins that the present invention uses is the phenolic resins of line style powdery, and particle diameter is 0.1-3mm.
Photochemical catalyst of the present invention is titanium dioxide (TiO
2), tungstic acid (WO
3), antimony oxide (Sb
2O
3), zirconium dioxide (ZrO
2), zinc oxide (ZnO) micro mist, can use wherein a kind also can use wherein two or more mixtures separately, be any proportioning during two or more mixing; Generally below 1 μ m, more little photocatalysis effect is good more for its particle diameter.TiO commonly used
2
The activator that the present invention uses is potassium hydroxide (KOH), zinc chloride (ZnCl
2), phosphoric acid (H
3PO
4) in any one or two kinds of above mixture, be any proportioning during two or more mixing, be technical grade.KOH commonly used.
The preparation method of aforesaid photochemical catalyst-phenolic resin-based activated carbon composite, its step is as follows:
(1) batching: the weight proportion of each constituent is: phenolic resins 40-100 part; Photochemical catalyst 10-50 part; Activating agent 20-100 part.
(2) carbonization: the line style powdered phenol-formaldehyde resin is mixed in proportion with photocatalyst powder, and levigate usefulness 200 orders sieve, the container of packing into, and under 400-600 ℃ of condition, under nitrogen protection, 1-4 hour charing powdered charcoal; The charing yield is between 60-80%.
(3) activation: with above powder charcoal; after activator fully mixes by weight; pack in the container; under nitrogen protection, under 400-600 ℃ of condition, after 2-4 hour activation of process finishes; with fully washing of goods cooling; remove alkali components, obtain product after the drying, can make fine powder and particle as required.Powder is 10-50 μ m, and particle is 1-4mm.
Aforesaid activator is an aqueous potassium hydroxide, and moisture content accounts for 15%.
Photocatalytic degradation appliance arrangement and technical process:
The photocatalytic degradation process as shown in Figure 2, (illumination is 53w/m with natural sunlight or ultraviolet lamp 1
2More than), be radiation source, in the container of agitator 2, add quantitative phenol wastewater 3, the back adds quantitative photochemical catalyst-phenolic resin-based activated carbon composite, start and stir and make that photochemical catalyst-phenolic resin-based activated carbon composite is all even to be dispersed in the phenol wastewater, through behind the certain hour, photochemical catalyst-phenolic resin-based activated carbon composite can progressively decompose the phenols noxious material of phenol wastewater.
After disposing, composite can be by the optic catalytic composite material that made that filters or the method for precipitation is separated with waste water, and through behind the UV-irradiation of a few hours, washing is reusable again.
The present invention utilizes linear phenol-aldehyde resin and photochemical catalyst break-in, in the process of intensification and carbonization, makes linear phenol-aldehyde resin urge agent closely to be impregnated in light, and photochemical catalyst is dispersed in the phenolic resins fat matrix activated carbon uniformly.Through after the activity, the catalytic surface that has further improved photochemical catalyst is long-pending, also can not block the surface hole defect of active carbon simultaneously.Improved the catalytic efficiency of photochemical catalyst greatly.
A certain proportion of composite powder is mixed with phenol wastewater, and under the irradiation of sunshine or ultraviolet light, photochemical catalyst produces strong OH, O
2Oxide group decomposes organic matter with the rich harmful phenol effect that concentrates on activated carbon surface, has eliminated the harm of organic phenol to environment.Outside this composite decapacitation Phenol-Containing Wastewater Treatment, can also handle some common organic poisonous wastewaters, as contain benzene, contain organic agricultural chemicals, contain organic sulfur compound waste water etc.
This composite raw material is wide, cheap, production process simple production cost is lower, the ability that shows optic catalytic composite material absorption, photocatalysis Decomposition organic poisonous wastewater by the result to phenol wastewater is stronger, and do not produce secondary pollution, after this material is regenerated through ultraviolet lighting-washing, can reuse, be a kind of novel surrounding purifying material.
Description of drawings
Fig. 1 is preparation technology figure of the present invention
Fig. 2 is a photocatalytic degradation procedure chart of the present invention
Among the figure: 1-ultraviolet lamp, 2-agitator, 3-phenol wastewater.
The specific embodiment
Embodiment 1: the phenolic resins of line taking type by weight powder 70 weight portions, photochemical catalyst (TiO
2) micro mist 35 weight portions, activator (KOH) 70 weight portions.The phenolic resins powder is mixed with the photochemical catalyst micro mist; grind in the container of packing into after 200 orders sieve; under nitrogen protection; carbonization is 3 hours under 500 ℃ of conditions; with above raw material of wood-charcoal that obtains and 35 weight portion activating agents (KOH); fully mix; pack in the container, under nitrogen protection, under 550 ℃ of conditions; activation in 2 hours; after activation finishes, being ground into photochemical catalyst-phenolic resin composite powder behind the washing and drying, is in the phenol wastewater of 1g/L in concentration; add the photocatalyst compound material identical and stir, at ultraviolet light (intensity 53w/m with the weight of phenol
2), irradiation in 8 hours, the decomposition amount (decomposition amount of phenol) of measuring phenol reaches more than 51.3%.The results are shown in Table 1.
Embodiment 2: the phenolic resins of line taking type by weight powder 70 weight portions, photochemical catalyst (WO
3) 35 weight portions, activator (zinc chloride) 35 weight portions, the method for manufacturing technology of pressing the optic catalytic composite material of enforcement 1 can obtain photochemical catalyst (WO
3) composite, press the method for the Phenol-Containing Wastewater Treatment of embodiment 1, the decomposition amount of measuring phenol can reach 47.8%, the results are shown in Table 1.
Embodiment 3: the phenolic resins of line taking type by weight 100 weight portions, photochemical catalyst (TiO
2) 10 weight portions, 100 parts in activator (KOH), 5 parts of zinc chloride, the method for manufacturing technology of pressing the photocatalyst compound material of embodiment 1 can obtain photochemical catalyst (TiO
2) composite, the decomposition amount of measuring phenol by the method for the processing phenol waste water of embodiment 1 can reach 37.5%.The results are shown in Table 1.
Embodiment 4: the phenolic resins of line taking type by weight 50 weight portions, photochemical catalyst (TiO
2) 50 weight portions, activating agent (KOH) 50 weight portions.Press the photocatalyst compound material manufacturing process method of embodiment 1, can obtain photochemical catalyst (TiO
2) composite, the decomposition amount of measuring phenol by the method for the Phenol-Containing Wastewater Treatment of embodiment 1 can reach 45%.The results are shown in Table 1.
Embodiment 5: the phenolic resins of line taking type by weight 60 weight portions, photochemical catalyst (TiO
210 weight fraction, WO
31 weight portion, Sb
2O
31 weight portion, ZnO1 weight portion, ZrO
21 weight portion), activating agent (KOH) 120 weight portions, the manufacturing process method of pressing the optic catalytic composite material of embodiment 1 can obtain light and urge composite, presses the method for the Phenol-Containing Wastewater Treatment of embodiment 1, and the decomposition amount of phenol can reach 39%, the results are shown in Table 1.
The different photocatalyst compound materials of table 1 are to the resolution ratio of phenol
| Time h embodiment | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 |
| ????1 | ??44％ | ??45％ | ??46％ | ??47％ | ??48％ | ??49％ | ??50％ | ??51.3％ |
| ????2 | ??45％ | ??45.5％ | ??46.1％ | ??46.5％ | ??46.9％ | ??47.5％ | ??47.6％ | ??47.8％ |
| ????3 | ??27％ | ??28.5％ | ??30％ | ??31.5％ | ??33％ | ??34.5％ | ??36％ | ??37.5％ |
| ????4 | ??35％ | ??38％ | ??41％ | ??43％ | ??43.5％ | ??44％ | ??44.5％ | ??45％ |
| ????5 | ??27％ | ??29％ | ??30％ | ??33％ | ??36％ | ??37％ | ??38％ | ??39％ |
Annotate 1: in the phenol solution of 1g/L, add optic catalytic composite material powder with phenol amount identical weight, use agitator, photocatalyst compound material is uniformly dispersed in waste water, under the irradiation of ultraviolet light, measured one time solution residue phenol weight every 1 hour.
Annotate 2: the method for testing of phenol content adopts GB GB7130-86 iodometric determination in the solution.
Claims (8)
1. photochemical catalyst-phenolic resin-based activated carbon composite, it is characterized in that: it comprises phenolic resins, photochemical catalyst and activating agent, the weight proportion of each constituent is: phenolic resins 40-100 part; Photochemical catalyst 10-50 part; Activating agent 20-100 part.
2. photochemical catalyst according to claim 1-phenolic resin-based activated carbon composite is characterized in that: described phenolic resins is the phenolic resins of line style powdery, and particle diameter is 0.1-3mm.
3. photochemical catalyst according to claim 1-phenolic resin-based activated carbon composite, it is characterized in that: described photochemical catalyst is any one or two kinds of above mixture in titanium dioxide, tungstic acid, antimony oxide, zirconium dioxide, the zinc oxide ultra_fine powders, is any proportioning during two or more mixing; Its particle diameter is below 1 μ m.
4. according to claim 1 or 3 described photochemical catalyst-phenolic resin-based activated carbon composites, it is characterized in that: described photochemical catalyst is best to be titanium dioxide.
5. photochemical catalyst according to claim 1-phenolic resin-based activated carbon composite is characterized in that: described activator is any one or two kinds of above mixture in potassium hydroxide, zinc chloride, the phosphoric acid, is any proportioning during two or more mixing.
6. photochemical catalyst-phenolic resin-based activated carbon composite according to claim 1 or 5 is characterized in that: described activator is best to be potassium hydroxide.
7. the preparation method of photochemical catalyst as claimed in claim 1-phenolic resin-based activated carbon composite is characterized in that: realized by following steps:
(1) batching: the weight proportion of each constituent is: phenolic resins 40-100 part; Photochemical catalyst 10-50 part; Activating agent 20-100 part;
(2) carbonization: the line style powdered phenol-formaldehyde resin is mixed in proportion with photocatalyst powder, and levigate usefulness 200 orders sieve, the container of packing into, and under 400-600 ℃ of condition, under nitrogen protection, 1-4 hour charing powdered charcoal;
(3) activation: with above powder charcoal; in proportion with after activator fully mixes; pack in the container; under nitrogen protection, under 400-600 ℃ of condition, after 2-4 hour activation of process finishes; with fully washing of goods cooling; remove alkali components, obtain product after the drying, can make fine powder and particle as required.
8. the preparation method of photochemical catalyst according to claim 7-phenolic resin-based activated carbon composite is characterized in that: described activator is an aqueous potassium hydroxide, and moisture content accounts for 15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125428 CN1235679C (en) | 2003-09-18 | 2003-09-18 | Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof |
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|---|---|---|---|
| CN 03125428 CN1235679C (en) | 2003-09-18 | 2003-09-18 | Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1524611A true CN1524611A (en) | 2004-09-01 |
| CN1235679C CN1235679C (en) | 2006-01-11 |
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ID=34285897
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|---|---|---|---|
| CN 03125428 Expired - Fee Related CN1235679C (en) | 2003-09-18 | 2003-09-18 | Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof |
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| CN (1) | CN1235679C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022641A1 (en) * | 2008-08-23 | 2010-03-04 | 比亚迪股份有限公司 | Plastic composition and method of selective metallization on the surface thereof |
| CN103240110A (en) * | 2013-05-29 | 2013-08-14 | 福建省林业科学研究院 | Iron and nitrogen co-doping titanium dioxide/active carbon photocatalyst |
| CN103240069A (en) * | 2013-05-29 | 2013-08-14 | 福建省林业科学研究院 | Titanium dioxide/active carbon photocatalyst and preparation method and application thereof |
| CN103977780A (en) * | 2014-06-06 | 2014-08-13 | 黑龙江大学 | Method for preparing mesoporous carbon loaded TiO2 (titanium dioxide) photocatalysis material in two-step hydrothermal method |
| CN106430187A (en) * | 2016-09-20 | 2017-02-22 | 湖南南方搏云新材料股份有限公司 | Method of using uncured carbon felt leftover material for preparing supercapacitor electrode activated carbon |
| CN107398259A (en) * | 2017-08-15 | 2017-11-28 | 德阳护球环保科技有限公司 | Volatile organic matter adsorbent for industrial waste gas processing |
| CN108620095A (en) * | 2018-05-16 | 2018-10-09 | 扬州工业职业技术学院 | A kind of composite catalyst and its application in synthetic glycerine aldehyde |
| CN109052731A (en) * | 2018-09-14 | 2018-12-21 | 杭州开源环保工程有限公司 | A method of efficiently removing antimony from dyeing waste water |
| CN111185231A (en) * | 2019-12-30 | 2020-05-22 | 哈尔滨工业大学（深圳） | Preparation of phenolic resin photocatalyst and its sterilization and disinfection method |
-
2003
- 2003-09-18 CN CN 03125428 patent/CN1235679C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022641A1 (en) * | 2008-08-23 | 2010-03-04 | 比亚迪股份有限公司 | Plastic composition and method of selective metallization on the surface thereof |
| CN103240110A (en) * | 2013-05-29 | 2013-08-14 | 福建省林业科学研究院 | Iron and nitrogen co-doping titanium dioxide/active carbon photocatalyst |
| CN103240069A (en) * | 2013-05-29 | 2013-08-14 | 福建省林业科学研究院 | Titanium dioxide/active carbon photocatalyst and preparation method and application thereof |
| CN103240069B (en) * | 2013-05-29 | 2015-03-25 | 福建省林业科学研究院 | Titanium dioxide/active carbon photocatalyst and preparation method and application thereof |
| CN103977780A (en) * | 2014-06-06 | 2014-08-13 | 黑龙江大学 | Method for preparing mesoporous carbon loaded TiO2 (titanium dioxide) photocatalysis material in two-step hydrothermal method |
| CN103977780B (en) * | 2014-06-06 | 2016-01-20 | 黑龙江大学 | Two one-step hydrothermals prepare mesoporous carbon-loaded TiO 2the method of catalysis material |
| CN106430187A (en) * | 2016-09-20 | 2017-02-22 | 湖南南方搏云新材料股份有限公司 | Method of using uncured carbon felt leftover material for preparing supercapacitor electrode activated carbon |
| CN107398259A (en) * | 2017-08-15 | 2017-11-28 | 德阳护球环保科技有限公司 | Volatile organic matter adsorbent for industrial waste gas processing |
| CN108620095A (en) * | 2018-05-16 | 2018-10-09 | 扬州工业职业技术学院 | A kind of composite catalyst and its application in synthetic glycerine aldehyde |
| CN108620095B (en) * | 2018-05-16 | 2020-09-29 | 扬州工业职业技术学院 | Composite catalyst and application thereof in synthesis of glyceraldehyde |
| CN109052731A (en) * | 2018-09-14 | 2018-12-21 | 杭州开源环保工程有限公司 | A method of efficiently removing antimony from dyeing waste water |
| CN111185231A (en) * | 2019-12-30 | 2020-05-22 | 哈尔滨工业大学（深圳） | Preparation of phenolic resin photocatalyst and its sterilization and disinfection method |
| CN111185231B (en) * | 2019-12-30 | 2023-03-10 | 哈尔滨工业大学（深圳） | Preparation of phenolic resin photocatalyst and its sterilization and disinfection method |
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| Publication number | Publication date |
|---|---|
| CN1235679C (en) | 2006-01-11 |
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