CN102380409B - Catalyst for effectively damaging cyanide and preparation method thereof - Google Patents
Catalyst for effectively damaging cyanide and preparation method thereof Download PDFInfo
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- CN102380409B CN102380409B CN 201110248352 CN201110248352A CN102380409B CN 102380409 B CN102380409 B CN 102380409B CN 201110248352 CN201110248352 CN 201110248352 CN 201110248352 A CN201110248352 A CN 201110248352A CN 102380409 B CN102380409 B CN 102380409B
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- molecular sieve
- catalyst
- cyanide
- type molecular
- ozone
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- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a catalyst for effectively damaging cyanide, wherein the catalyst is obtained by flashing an X- type molecular sieve on which nickel ions are uniformly distributed at high temperature. The invention further discloses a preparation method of the catalyst for effectively damaging cyanide, comprising the following steps: taking substance with the nickel ions to prepare as liquor according to the 2%-3% concentration; dipping the X- type molecular sieve in the liquor so that the nickel ions are uniformly distributed on the surface of the X- type molecular sieve; pouring out the upper liquor, washing the X- type molecular sieve with clean water for multiple times, then drying, and flashing at high temperature to obtain the catalyst. The reaction speed is quickened through adding the nickel supported X- type molecular sieve catalyst while damaging cyanide with ozone, and the removing efficiency of the cyanide is improved, so the high efficiency catalytic action while damaging the cyanide with ozone is realized.
Description
Technical field
The present invention relates to the electroplating wastewater processing field, particularly relate to a kind of Catalysts and its preparation method of efficient broken cyanide.
Background technology
The waste water that produces in electroplating process can produce great harm to natural environment, cyanide wastewater wherein is a kind of industrial wastewater that has toxicity, in order to make it can not produce harm to natural environment, it is processed an important process process that becomes in the electroplating wastewater processing process.One of major technique that cyanide wastewater is processed is exactly to make its cyanide structural deterioration, i.e. broken cyanide; In the processing method of present electroplating cyanic waste water, the clorox broken cyanide of commonly using, but the method chemical feeding quantity is large, processes deficiencies such as having the accessory substance generation.
The ozone oxidation non-secondary pollution does not produce mud and odor smell, so there is larger prospect in the application of ozone broken cyanide.The principle of ozone broken cyanide is: the chemism of ozone Oxidation Treatment cyanide and rhodanate is:
CN
-+O
3→CNO
-+O
2↑(1)
2CNO
-+3O
3+H
2O→N
2↑+2HCO
3 -+3O
2(2)
2SCN
-+11O
3+4OH
-→2HCO
3 -+2SO
3 -+N
2↑+3H
2O+11O
2↑(3)
But ozone can only be Fe (CN) to the cyanogen non-oxidation ability in iron, ferrocyanide
6 4-Be oxidized to Fe (CN)
6 3-, therefore contain Fe (CN) in waste water
6 4-The time, the Ozonation effect is undesirable.
Summary of the invention
For the problems referred to above, purpose of the present invention is providing a kind of removal efficient that can improve cyanide, particularly effectively removes the Catalysts and its preparation method of the cyanogen in iron, ferrocyanide.
For achieving the above object, technical scheme proposed by the invention is: a kind of catalyst of efficient broken cyanide is characterized in that: described catalyst is to be evenly distributed with the X-type molecular sieve of nickel ion by gained after the high temperature flash distillation.
The invention still further relates to the preparation method of the catalyst of above-mentioned efficient broken cyanide: get nickeliferous ionic species by 2%-3% concentration wiring solution-forming, X-type molecular sieve is immersed in this solution, nickel ion is evenly distributed on X-type molecular sieve surface, pour out upper solution, with clear water rinse X-type molecular sieve number all over after, oven dry is prepared from after the high temperature flash distillation.
Further, to be immersed in the time in solution be 24-36h to described X-type molecular sieve.
Further, described nickeliferous ionic species is nickelous sulfate, nickel halogenide etc.
Described catalyst broken cyanide principle of the present invention is: X-type molecular sieve itself has stronger catalytic action, and in general, Al/Si is than higher, and the specific activity of OH base is higher, and the Si/Al of X-type molecular sieve is 1-1.5, and is relatively low.X-type molecular sieve can provide very high activity and uncommon selective in various acid catalyst, show from the electron configuration of nickle atom, in the d band of nickel, some can not be filled, i.e. " d is with the hole ", d is with the existence in hole, make it to accept from the external world electronics and adsorbing species and the ability of Cheng Jian with it, but d band hole is not The more the better, in metal and alloy catalyst thereof, catalytic activity contrast: ambrose alloy＜nickel〉ferronickel, wherein, it is 0 that the d of copper is with the hole, it is 2.2 that the d of iron is with the hole, and it is 0.6 that the d of nickel is with the hole.Metallic catalyst evenly distributes on carrier surface, gives full play to its catalytic effect, for the catalyst of support type, ideal situation is: active component both had stronger interaction with carrier, be unlikely to again to be detained the reduction of metal, the reaction that has CO to participate in, activity is greatly improved.Ni-loaded catalyst sharply shows normal catalytic activity before flash distillation, and after the high temperature flash distillation, height of formation nonequilibrium point defect concentration in molecular sieve supported surface makes ni-loaded catalyst demonstrate superactivity.
For this reason, be chosen in ozone treatment cyanide wastewater device, add the Ni molecular sieve catalyst, the oxygen that cyanide wastewater utilizes the ozone broken cyanide to produce on the surface of molecular sieve catalyst carries out oxidation reaction, then accelerated the speed of ozone broken cyanide positive reaction, after adding in addition the high temperature flash distillation, the Ni molecular sieve catalyst demonstrates superactivity, ferrocyanide is attracted on molecular sieve, and is oxidized under its high activity, thereby improved the removal efficient of cyanide.Therefore, add the Ni molecular sieve catalyst in the ozone broken cyanide, not only accelerated reaction rate, and improved the removal efficient of cyanide, thereby reach the efficient catalytic effect of ozone broken cyanide.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1:(is take lab scale as example)
Get nickelous sulfate 10g, be dissolved in 500mL water, take 500gX-type molecular sieve in container, add in the 500mL nickel sulfate solution for preparing, after soaking 30h, pour out solution, nickel ion is distributed in X-type molecular sieve, clean X-type molecular sieve number time, after oven dry, the high temperature flash distillation gets catalyst, is used for the ozone broken cyanide.
Embodiment 2:(is take lab scale as example)
Get nickelous sulfate 15g, be dissolved in 500mL water, take 500gX-type molecular sieve in container, add in the 500mL nickel sulfate solution for preparing, after soaking 24h, pour out solution, nickel ion is distributed in X-type molecular sieve, clean X-type molecular sieve number time, after oven dry, the high temperature flash distillation gets catalyst, is used for the ozone broken cyanide.
Embodiment 3:(is take lab scale as example)
Get nickel chloride 12g, be dissolved in 500mL water, take 500gX-type molecular sieve in container, add in the 500mL nickel chloride solution for preparing, after soaking 36h, pour out solution, nickel ion is distributed in X-type molecular sieve, clean X-type molecular sieve number time, after oven dry, the high temperature flash distillation gets catalyst, is used for the ozone broken cyanide.
Catalyst broken cyanide embodiment 1
In ozone broken cyanide device, add the Ni molecular sieve catalyst 500g for preparing, add 50L to contain cyanogen water, regulating former water pH is 9.0 left and right, with batch (-type) processing mode broken cyanide, passes into ozone, to processing running time and Operation results analysis, and compare with not adding catalyst ozone broken cyanide, its Central Plains water condition and ozone intake condition are identical, and experimental result sees the following form:
Although specifically show and introduced the present invention in conjunction with preferred embodiment; but the those skilled in the art should be understood that; within not breaking away from the spirit and scope of the present invention that appended claims limits; in the form and details the present invention is made a variety of changes, be protection scope of the present invention.
Claims (3)
1. the method for preparing catalyst of an efficient broken cyanide, it is characterized in that: described preparation method's step is: get nickeliferous ionic species by 2%-3% concentration wiring solution-forming, X-type molecular sieve is immersed in this solution, nickel ion is evenly distributed on X-type molecular sieve surface, pour out upper solution, with clear water rinse X-type molecular sieve number all over after, oven dry, be prepared from after the high temperature flash distillation, the time that described X-type molecular sieve is immersed in solution is 24-36h.
2. the method for preparing catalyst of a kind of efficient broken cyanide according to claim 1, it is characterized in that: described nickeliferous ionic species is nickelous sulfate.
3. the method for preparing catalyst of a kind of efficient broken cyanide according to claim 1, it is characterized in that: described nickeliferous ionic species is nickel halogenide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110248352 CN102380409B (en) | 2011-08-25 | 2011-08-25 | Catalyst for effectively damaging cyanide and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110248352 CN102380409B (en) | 2011-08-25 | 2011-08-25 | Catalyst for effectively damaging cyanide and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102380409A CN102380409A (en) | 2012-03-21 |
| CN102380409B true CN102380409B (en) | 2013-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110248352 Expired - Fee Related CN102380409B (en) | 2011-08-25 | 2011-08-25 | Catalyst for effectively damaging cyanide and preparation method thereof |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541019A (en) * | 2015-12-28 | 2016-05-04 | 天津凯英科技发展有限公司 | Treatment method of high-concentration oil-containing cyanide-containing wastewater |
| CN114130403B (en) * | 2021-11-25 | 2024-01-05 | 深圳科力迩科技有限公司 | Composite catalytic material and method for treating black and odorous water body |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743381A (en) * | 1987-07-01 | 1988-05-10 | Fmc Corporation | Process for oxidizing a cyanide compound |
| CN102019208A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Continuous steeping method for grain carrier and equipment thereof |
-
2011
- 2011-08-25 CN CN 201110248352 patent/CN102380409B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743381A (en) * | 1987-07-01 | 1988-05-10 | Fmc Corporation | Process for oxidizing a cyanide compound |
| CN102019208A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Continuous steeping method for grain carrier and equipment thereof |
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| Publication number | Publication date |
|---|---|
| CN102380409A (en) | 2012-03-21 |
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Owner name: VISBE (XIAMEN) ENVIRONMENTAL TECHONLOGY CO., LTD. Free format text: FORMER NAME: XIAMEN VISBE FILM TECHNOLOGY CO., LTD. |
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Address after: 101, 17, 102, Xiang Yue Road, 361000 torch hi tech Zone (Xiangan) Industrial Zone, Fujian, Xiamen Patentee after: XIAMEN VISBE MEMBRANE TECHNOLOGY CO., LTD. Address before: 101, 17, 102, Xiang Yue Road, 361000 torch hi tech Zone (Xiangan) Industrial Zone, Fujian, Xiamen Patentee before: Xiamen Visbe Membrane Technology Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130612 Termination date: 20160825 |