CN103301887A - Catalyst for treating chorine-containing organic matters in water and preparation method thereof - Google Patents
Catalyst for treating chorine-containing organic matters in water and preparation method thereof Download PDFInfo
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- CN103301887A CN103301887A CN 201310183019 CN201310183019A CN103301887A CN 103301887 A CN103301887 A CN 103301887A CN 201310183019 CN201310183019 CN 201310183019 CN 201310183019 A CN201310183019 A CN 201310183019A CN 103301887 A CN103301887 A CN 103301887A
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Abstract
The invention relates to a catalyst and a preparation method thereof, and particularly relates to a catalyst for treating chorine-containing organic matters in water and a preparation method thereof. According to the catalyst for treating chorine-containing organic matters in water, active components comprise four metals, namely bismuth, palladium, platinum and ruthenium, a carrier is a titanium dioxide/activated carbon composite carrier, and 0.15% of polytetrafluoroethylene is contained on the surface of the catalyst. The invention further provides a method for preparing the catalyst, the catalyst is adopted for removing 4-chlorophenol in wastewater by adopting an electrochemical reduction and oxidation combination method, and tests prove that by adopting the catalyst of the embodiment, the conversion rate of the 4-chlorophenol in the wastewater can achieve 100%, the dechlorination rate can achieve 100%, the removal rate of total organic carbon (TOC) can achieve 88.7%, and the catalyst further has great activity.
Description
Technical field
The present invention relates to Catalysts and its preparation method, particularly the organic Catalysts and its preparation method of a kind of processing water containing chlorine.
Background technology
Organic chlorine agriculture chemicals, such as BHC and DDT etc., disease and pest is had wide spectrum and efficient kill activity, used on a large scale in one's early years, because its stable chemical nature, degradation speed is slow, heat-resisting acidproof, easily residual, can enter human body by the effect of accumulating with food chain in the animal and plant body, pollution of circulation can reach 20～30 years in biological chain, causes the very big harm to health.China bans use of this type of agricultural chemicals in nineteen eighty-three, but still can detect organic chlorine agriculture chemicals at present in many agricultural product.
All more or less there are some defectives in the biodegrading process that common are at present machine chlorine class agricultural chemicals: (1) utilizes the microbial degradation selectivity ratios higher, but the cultivation of bacterial classification bothers very much, bacterial classification is very strict to the requirement of temperature when degraded, only under its best temperature, higher degradation rate is arranged, the extensive relatively difficulty of utilizing; (2) utilize the ozone oxidation degraded to have broad spectrum activity, but also can destroy active ingredient simultaneously, therefore relatively be fit to Industrial Wastewater Treatment, the required time of degrading in addition is long, and the manufacturing expense of ozone is higher.(3) utilize mechanical ball milling dechlorination to be fit to solid powder substance, normally in argon atmosphere, CaO is in the same place ball milling in cylinder of steel with the pastille mixing of materials, after more than ten hours, can substantially remove the chloro pesticide that contains in the material, the method length consuming time, somewhat expensive, applicable surface is narrow; (4) utilize Photocatalyst to have a extensive future, this method utilizes the electronics-hole with redox ability that photochemical catalyst produces under action of ultraviolet light to object is effectively decomposed, mostly utilize the water slurry of nano TiO 2 to come agricultural chemicals in the catalytic degradation aqueous solution in the document, Main Problems has two, the one, catalysis material is difficult to recycle even produce thus secondary pollution, and the 2nd, the degraded of single nano material is selectively not high.
Summary of the invention
The object of the present invention is to provide a kind of environmental friendliness, non-secondary pollution, selective high chlorine organic Catalysts and its preparation method.Technical scheme is as follows.
The organic catalyst of a kind of processing water containing chlorine, active constituent are bismuth, palladium, platinum, four kinds of metals of ruthenium, and carrier is titanium dioxide/activated carbon composite carrier, contains 0.15～0.2% polytetrafluoroethylene (PTFE) at catalyst surface.
A kind of preparation method who processes the organic catalyst of water containing chlorine comprises the steps:
(1) active carbon and nano titanium dioxide powder in mass ratio 1:1 fully mix, add concentration and be 30% glycol water, strong stirring obtains the mixed solution of the carrier that active carbon and titanium dioxide forms;
(2) Bi (NO3) 3, PdCl2, ruthenic chloride are dissolved in the hydrochloric acid, make mixed liquor, in described mixed liquor, add the mixed solution of step (1), and the pH value is remained in the scope of 0.3-1.0, stir and obtain mixed serum;
(3) H2PtCl66H2O is dissolved in the ethanol, makes platinum solution and be added drop-wise in the mixed serum that step (2) obtains, stir and obtain bismuth-palladium-platinum-ruthenium charcoal slurries;
(4) reduce described bismuth-palladium-platinum-ruthenium charcoal slurries, adopt sodium formate as reducing agent, 100～150 ℃ of reduction temperatures, the recovery time is 1～8 hour;
(5) through cooling, after the centrifugation, with pure water washing gained solid matter;
(6) will reduce good catalyst 100～120 ℃ of dryings 24 hours, then will polytetrafluoroethylene (PTFE) spray to catalyst surface, 100 ℃ of dryings 20 hours, namely get the organic catalyst of described processing water containing chlorine at last.
The inventive method both can be used for processing the various industrial wastewaters that contain organic chlorine agriculture chemicals, also can be used for processing the organochlorine class remains of pesticide in the agricultural product water extracts such as grain, fruit, tealeaves or Chinese herbal medicine.Accessible organic chlorine agriculture chemicals comprises BHC BHC, DDT DDT, heptachlor HC, hexachlorobenzene HCB, drinox ALD, pentachloronitrobenzene PCNB, Niran CD etc.
The specific embodiment
In order better to understand and to implement, describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
The organic catalyst of a kind of processing water containing chlorine, active constituent are bismuth, palladium, platinum, four kinds of metals of ruthenium, and carrier is TiO
2/ activated carbon composite carrier contains 0.2% polytetrafluoroethylene (PTFE) at catalyst surface.
Above-mentioned catalyst is made by following preparation method:
(1) active carbon and nano-TiO
2Powder in mass ratio 1:1 fully mixes, and adding concentration is 30% glycol water, and strong stirring obtains active carbon and TiO
2The mixed solution of the carrier that forms;
(2) with Bi (NO
3)
3, PdCl
2, ruthenic chloride is dissolved in the hydrochloric acid, makes mixed liquor, adds the mixed solution of step (1) in the described mixed liquor, and the pH value remained in 0.8 the scope, stir and obtain mixed serum;
(3) with H
2PtCl
66H
2O is dissolved in the ethanol, makes platinum solution and is added drop-wise in the mixed serum that step (2) obtains, and stirs and obtains bismuth-palladium-platinum-ruthenium charcoal slurries;
(4) reduce described bismuth-palladium-platinum-ruthenium charcoal slurries, adopt sodium formate as reducing agent, 120 ℃ of reduction temperatures, the recovery time is 5 hours;
(5) through cooling, after the centrifugation, with pure water washing gained solid matter;
(6) will reduce good catalyst 120 ℃ of dryings 24 hours, then will polytetrafluoroethylene (PTFE) spray to catalyst surface, 100 ℃ of dryings 20 hours, namely get the organic catalyst of described processing water containing chlorine at last.
The method of employing electrochemical reduction and oxidation bonding is removed the 4-chlorophenol in the waste water, concrete steps adopt known method to get final product, after tested, adopt the catalyst of the present embodiment, the conversion ratio of 4-chlorophenol can reach 100% in the waste water, dechlorination rate reaches 100%, and total organic carbon (TOC) clearance can reach 87.5%, has good activity.
Embodiment 2
The organic catalyst of a kind of processing water containing chlorine, active constituent are bismuth, palladium, platinum, four kinds of metals of ruthenium, and carrier is TiO
2/ activated carbon composite carrier contains 0.15% polytetrafluoroethylene (PTFE) at catalyst surface.
Above-mentioned catalyst is made by following preparation method:
(1) active carbon and nano-TiO
2Powder in mass ratio 1:1 fully mixes, and adds concentration and be 30% glycol water, and strong stirring obtains the mixed solution of the carrier that active carbon and TiO2 form;
(2) with Bi (NO
3)
3, PdCl
2, ruthenic chloride is dissolved in the hydrochloric acid, makes mixed liquor, adds the mixed solution of step (1) in the described mixed liquor, and the pH value remained in 0.5 the scope, stir and obtain mixed serum;
(3) with H
2PtCl
66H
2O is dissolved in the ethanol, makes platinum solution and is added drop-wise in the mixed serum that step (2) obtains, and stirs and obtains bismuth-palladium-platinum-ruthenium charcoal slurries;
(4) reduce described bismuth-palladium-platinum-ruthenium charcoal slurries, adopt sodium formate as reducing agent, 100～150 ℃ of reduction temperatures, the recovery time is 3 hours;
(5) through cooling, after the centrifugation, with pure water washing gained solid matter;
(6) will reduce good catalyst 100 ℃ of dryings 24 hours, then will polytetrafluoroethylene (PTFE) spray to catalyst surface, 100 ℃ of dryings 20 hours, namely get the organic catalyst of described processing water containing chlorine at last.
The method of employing electrochemical reduction and oxidation bonding is removed the 4-chlorophenol in the waste water, concrete steps adopt known method to get final product, after tested, adopt the catalyst of the present embodiment, the conversion ratio of 4-chlorophenol can reach 100% in the waste water, dechlorination rate reaches 100%, and total organic carbon (TOC) clearance can reach 88.7%, has good activity.
Above-described embodiment is to explanation of the present invention, is not limitation of the invention, any scheme after the simple transformation of the present invention is all belonged to protection scope of the present invention.
Claims (2)
1. process the organic catalyst of water containing chlorine for one kind, it is characterized in that, active constituent is bismuth, palladium, platinum, four kinds of metals of ruthenium, and carrier is titanium dioxide/activated carbon composite carrier, contains 0.15～0.2% polytetrafluoroethylene (PTFE) at catalyst surface.
2. a preparation method who processes the organic catalyst of water containing chlorine is characterized in that, comprises the steps:
(1) active carbon and nano titanium dioxide powder in mass ratio 1:1 fully mix, add concentration and be 30% glycol water, strong stirring obtains the mixed solution of the carrier that active carbon and titanium dioxide forms;
(2) with Bi (NO
3)
3, PdCl
2, ruthenic chloride is dissolved in the hydrochloric acid, makes mixed liquor, adds the mixed solution of step (1) in described mixed liquor, and the pH value remained in the scope of 0.3-1.0, stir and obtain mixed serum;
(3) with H
2PtCl
66H
2O is dissolved in the ethanol, makes platinum solution and is added drop-wise in the mixed serum that step (2) obtains, and stirs and obtains bismuth-palladium-platinum-ruthenium charcoal slurries;
(4) reduce described bismuth-palladium-platinum-ruthenium charcoal slurries, adopt sodium formate as reducing agent, 100～150 ℃ of reduction temperatures, the recovery time is 1～8 hour;
(5) through cooling, after the centrifugation, with pure water washing gained solid matter;
(6) will reduce good catalyst 100～120 ℃ of dryings 24 hours, then will polytetrafluoroethylene (PTFE) spray to catalyst surface, 100 ℃ of dryings 20 hours, namely get the organic catalyst of described processing water containing chlorine at last.
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| CN 201310183019 CN103301887A (en) | 2013-05-16 | 2013-05-16 | Catalyst for treating chorine-containing organic matters in water and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888401A (en) * | 2015-05-20 | 2015-09-09 | 中国科学院新疆理化技术研究所 | Method for dechlorination from chlorophenol pollutant by using alkali metal zinc borate compound via photocatalysis |
| CN106186597A (en) * | 2016-07-11 | 2016-12-07 | 许祚员 | A kind of drinox Contaminated Sewage Sludge inorganic agent and preparation method thereof |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN107892375A (en) * | 2017-10-19 | 2018-04-10 | 上海交通大学 | The minimizing technology of chloride Chlorine in Solution ion |
| CN109317172A (en) * | 2018-11-07 | 2019-02-12 | 东北师范大学 | A kind of preparation method and application of platinum-titanium dioxide/phosphotungstic acid composite membrane |
| CN114260011A (en) * | 2022-01-05 | 2022-04-01 | 贵州师范大学 | Preparation method of ruthenium-iridium-titanium-platinum-doped quaternary photoelectrocatalysis carbon-based electrode |
| CN115722272A (en) * | 2022-12-07 | 2023-03-03 | 四川轻化工大学 | Preparation method and application of high-stability core-shell structure hydrodechlorination catalyst |
-
2013
- 2013-05-16 CN CN 201310183019 patent/CN103301887A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888401A (en) * | 2015-05-20 | 2015-09-09 | 中国科学院新疆理化技术研究所 | Method for dechlorination from chlorophenol pollutant by using alkali metal zinc borate compound via photocatalysis |
| CN106186597A (en) * | 2016-07-11 | 2016-12-07 | 许祚员 | A kind of drinox Contaminated Sewage Sludge inorganic agent and preparation method thereof |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN107892375A (en) * | 2017-10-19 | 2018-04-10 | 上海交通大学 | The minimizing technology of chloride Chlorine in Solution ion |
| CN107892375B (en) * | 2017-10-19 | 2021-08-06 | 上海交通大学 | Method for removing chloride ions in chlorine-containing solution |
| CN109317172A (en) * | 2018-11-07 | 2019-02-12 | 东北师范大学 | A kind of preparation method and application of platinum-titanium dioxide/phosphotungstic acid composite membrane |
| CN114260011A (en) * | 2022-01-05 | 2022-04-01 | 贵州师范大学 | Preparation method of ruthenium-iridium-titanium-platinum-doped quaternary photoelectrocatalysis carbon-based electrode |
| CN114260011B (en) * | 2022-01-05 | 2023-09-12 | 贵州师范大学 | Preparation method of ruthenium iridium titanium platinum doped quaternary photoelectrocatalysis carbon-based electrode |
| CN115722272A (en) * | 2022-12-07 | 2023-03-03 | 四川轻化工大学 | Preparation method and application of high-stability core-shell structure hydrodechlorination catalyst |
| CN115722272B (en) * | 2022-12-07 | 2024-03-26 | 四川轻化工大学 | Preparation method and application of high-stability core-shell structure hydrodechlorination catalyst |
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Application publication date: 20130918 |