CN103801297B - A kind of Preparation method and use of copper nickel compoilite oxide catalyst - Google Patents
A kind of Preparation method and use of copper nickel compoilite oxide catalyst Download PDFInfo
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- CN103801297B CN103801297B CN201210463923.1A CN201210463923A CN103801297B CN 103801297 B CN103801297 B CN 103801297B CN 201210463923 A CN201210463923 A CN 201210463923A CN 103801297 B CN103801297 B CN 103801297B
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- oxide catalyst
- compoilite
- copper nickel
- clorox
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 25
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- LDSIKPHVUGHOOI-UHFFFAOYSA-N copper;oxonickel Chemical compound [Ni].[Cu]=O LDSIKPHVUGHOOI-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 49
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 16
- 238000000354 decomposition reaction Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000011780 sodium chloride Substances 0.000 abstract description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 150000002815 nickel Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000010792 warming Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention discloses a kind of preparation method of copper nickel oxide catalyst, comprise the steps: 1) by nickel salt, mantoquita and highly basic by 1: 1: 4.5 molar ratio mix after soluble in waterly make mixed aqueous solution; 2) precursor solution is obtained after mixed aqueous solution at room temperature being stirred 6 ~ 10 hours; 3) under precursor solution being warming up to 120 DEG C ~ 140 DEG C conditions, reaction obtains reactant liquor in 8 ~ 16 hours; 4), after reaction terminates, reactant liquor is naturally cooled to room temperature; 5) reactant liquor is carried out filtration and obtain filtrate; 6) by filtrate cleaning, drying, copper nickel compoilite oxide catalyst is obtained.Copper nickel compoilite oxide catalyst catalytic performance prepared by the present invention obtains large lifting, overcomes the feature that single structure catalytic activity is weak, simultaneously raw materials used cheap, and process for producing is simple, has the advantage that cost is low; Copper nickel compoilite oxide catalyst is to the catalytic decomposition excellent performance of clorox, and decomposition efficiency is high, speed is fast, clorox can be decomposed into harmless sodium chloride and oxygen.
Description
Technical field
The present invention relates to a kind of chemical catalyst, especially relate to a kind of Preparation method and use of copper nickel compoilite oxide catalyst.
Background technology
Clorox (NaClO) is a kind of broad-spectrum raw material of industry, because it all has stronger oxidisability in acidity, weakly alkaline solution, is commonly used for disinfectant, bleaching agent; Liquor natrii hypochloritis is for the treatment of waste water, the object of oxidation Decomposition pollutant, bleaching, sterilizing, deodorization can be reached, but in processing procedure, usually due to compound that clorox is unstable, easily there is photolysis reactions in temperature under higher or solar radiation, easily generate NaClO
3, NaCl, HCl etc., greatly reduce the utilization rate of clorox strong oxidizing property, the HCl gas simultaneously produced in decomposable process causes very large harm to environment, if generate environment amenable oxygen when making clorox decompose in turn enhance its oxidation susceptibility, this will make this problem be settled properly.
Clorox is also the harmful side product of chlor-alkali plant, metallurgy industry, needs to carry out Non-toxic process.Chlor-alkali and metallurgy industry produce in exhaust gas containing a large amount of chlorine, chlorine, as noxious material, needs to carry out necessary process before discharging, and method conventional is at present that the product of neutralization is clorox with the chlorine in sodium hydroxide solution and in waste gas.But the clorox generated is often because low, the impurity content of concentration is up to less than the value recycled, thus in producing all waste liquid directly discharge.The material that clorox is harmful to environmental toxic because its unstability can generate, excessive clorox can produce carcinogenic substance chloroform, in aqueous so being carried out resolution process is industrial necessarily requiring simultaneously.The general row acid decomposition of the generable isolation of clorox, thermal decomposition, light decompose and metal catalyzed decomposition.And clorox meets acid meeting fast decoupled decomposition generation chlorine again.It is slow that thermal decomposition and light decompose decomposition rate, can not meet industrial demand, can produce environmentally harmful NaClO simultaneously
3.And catalytic decomposition can make clorox be decomposed into environment amenable sodium chloride and oxygen, so it is the optimal path processing clorox problem that selective catalysis decomposes.Metal oxide has good catalytic effect to clorox, and the cartalytic decomposition effect of metal oxide (MeO) is as follows:
2MeO+NaClO＝Me
2O
3+NaCl
Me
2O
3+NaClO＝2MeO+NaCl+O
2
Although noble metal catalyst activity is higher, expensive, cost is high, is difficult to apply in actual production.The oxide of the metals such as manganese, copper, nickel has the effect of accelerated decomposition to clorox, be the ideal chose as catalyst.Nickel ion and copper ion and clorox can form good wrong fount, can realize the catalytic decomposition to clorox.But the oxide of independent copper and mickel needs higher temperature to the decomposition of clorox, and speed is slow, and efficiency is low, limits its application.The decomposition reaction of clorox is first order kinetics reaction, and reduction temperature and concentration can make the decomposition reaction velocity of NaClO slow down.And general in actual production what produce is the clorox of low temperature and low concentration, this requires that catalyst realizes fast decoupled feature under having low temperature, low consistency conditions.The composite oxide catalysts of copper and mickel can meet this requirement, and realizes quick, the efficient-decomposition of clorox.
Based on this, the present invention proposes a kind of composite oxide catalysts of copper and mickel, this catalyst has excellent catalytic performance, can make that clorox reaches fast, the effect of efficient-decomposition at low temperatures.
Summary of the invention
The present invention is to reduce and eliminating industrial harmful substance clorox to the harm of environment; a kind of composite oxide catalysts of copper and mickel is provided; this catalyst can make low concentration clorox under cryogenic rapidly and efficiently be decomposed into sodium chloride and oxygen, reach the object of environmental protection.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of copper nickel oxide catalyst, comprises the steps: 1) by nickel salt, mantoquita and highly basic by 1: 1: 4.5 molar ratio mix after soluble in waterly make mixed aqueous solution; 2) precursor solution is obtained after mixed aqueous solution at room temperature being stirred 6 ~ 10 hours; 3) under precursor solution being warming up to 120 DEG C ~ 140 DEG C conditions, reaction obtains reactant liquor in 8 ~ 16 hours; 4), after reaction terminates, reactant liquor is naturally cooled to room temperature; 5) reactant liquor is carried out filtration and obtain filtrate; 6) by filtrate cleaning, drying, copper nickel compoilite oxide catalyst is obtained.
As preferably, step 1) described in nickel salt be nickel nitrate.
As preferably, step 1) described in mantoquita be copper nitrate.
As preferably, step 1) described in highly basic be NaOH.
As preferably, step 2) described in room temperature be 20 DEG C ~ 25 DEG C.
As preferably, step 6) in filtrate cleaning adopt water to rinse.
As preferably, step 6) in filtrate baking temperature be 100 DEG C, drying time is 8 hours.
The purposes of the copper nickel compoilite oxide catalyst obtained by above step is: mass concentration be the aqueous sodium hypochlorite solution of 4 ~ 10% under the catalytic action of described copper nickel compoilite oxide catalyst, under 50 DEG C ~ 75 DEG C conditions reaction within 5 ~ 15 minutes, make clorox be decomposed into sodium chloride and oxygen; The consumption of described copper nickel compoilite oxide catalyst is 0.25 ~ 1.5% of liquor natrii hypochloritis's quality to be decomposed.
Compared with prior art, beneficial effect of the present invention is that (1) the present invention has prepared copper nickel compoilite oxide catalyst, copper nickel composite construction makes catalytic performance obtain large lifting, overcome the feature that single structure catalytic activity is weak, simultaneously raw materials used cheap, process for producing is simple, has the advantage that cost is low; (2) copper nickel compoilite oxide catalyst of the present invention is to the catalytic decomposition excellent performance of clorox, and decomposition efficiency is high, speed is fast, and clorox is decomposed into harmless sodium chloride and oxygen; Can make mass content be the liquor natrii hypochloritis of 8% under 60 DEG C of conditions, in 10 minutes, resolution ratio reaches more than 99%, fully meet in industrial production process clorox decompose needs.
Accompanying drawing explanation
Fig. 1 is a kind of X ray diffracting spectrum (XRD) preparing clorox decomposition copper nickel composite catalyst.
Fig. 2 is the time chart that under different temperatures, clorox resolution ratio reaches 99% correspondence.
Fig. 3 is the time chart that under different catalysts consumption, clorox resolution ratio reaches 99% correspondence.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but scope is not limited thereto:
Embodiment 1:
(1) 2.91g (0.01mol) Ni (NO is taken
3)
26H
2o and 2.42g (0.01mol) Cu (NO
3)
23H
2o 100ml deionized water dissolving, takes 1.8g (0.045mol) NaOH 100ml deionized water dissolving, NaOH solution is joined Ni (NO
3)
3with Cu (NO
3)
2mixed solution in, stirred at ambient temperature 8 hours, obtains precursor solution.
(2) join in 250ml hydrothermal reaction kettle by step (1) precursor solution, hydro-thermal reaction 10 hours at 130 DEG C, heating rate is 10 DEG C/min.
(3) after the reaction of step (2) completes, after question response liquid is naturally cold, by reacting liquid filtering, products in water cleans, by products therefrom in drying box under 100 DEG C of conditions dry 8 hours after cleaning, obtain black product copper nickel compoilite oxide catalyst.
Embodiment 2:
(1) 2.91g (0.01mol) Ni (NO is taken
3)
26H
2o and 2.42g (0.01mol) Cu (NO
3)
23H
2o 100ml deionized water dissolving, takes 1.8g (0.045mol) NaOH 100ml deionized water dissolving, NaOH solution is joined Ni (NO
3)
3with Cu (NO
3)
2mixed solution in, stirred at ambient temperature 8 hours, obtains precursor solution.
(2) join in 250ml hydrothermal reaction kettle by step (1) precursor solution, hydro-thermal reaction 10 hours at 120 DEG C, heating rate is 10 DEG C/min.
(3) after the reaction of step (2) completes, after question response liquid is naturally cold, by reacting liquid filtering, products in water cleans, by products therefrom in drying box under 100 DEG C of conditions dry 8 hours after cleaning, obtain black product copper nickel compoilite oxide catalyst.
Embodiment 3:
(1) 2.91g (0.01mol) Ni (NO is taken
3)
2.6H
2o and 2.42g (0.01mol) Cu (NO
3)
23H
2o 100ml deionized water dissolving, takes 1.8g (0.045mol) NaOH 100ml deionized water dissolving, NaOH solution is joined Ni (NO
3)
3with Cu (NO
3)
2mixed solution in, stirred at ambient temperature 8 hours, obtains precursor solution.
(2) join in 250ml hydrothermal reaction kettle by step (1) precursor solution, hydro-thermal reaction 10 hours at 140 DEG C, heating rate is 10 DEG C/min.
(3) after the reaction of step (2) completes, after question response liquid is naturally cold, by reacting liquid filtering, products in water cleans, by products therefrom in drying box under 100 DEG C of conditions dry 8 hours after cleaning, obtain black product copper nickel compoilite oxide catalyst.
Embodiment 4:
(1) configuration quality concentration is 8% liquor natrii hypochloritis 2000ml, measure 8% liquor natrii hypochloritis 6 parts of 300ml, it put into respectively the beaker of 500ml and be placed in water bath with thermostatic control to be heated to temperature be 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C; The copper nickel compoilite oxide catalyst taking 1.5g embodiment 1 respectively obtained joins in each beaker, reacting to not having to stop during bubble formation, recording the reaction time at each temperature under stirring condition.
(2) according to the content of clorox in solution after the method difference assaying reaction of GB19106-2003, calculate resolution ratio, in all reactant liquors, clorox resolution ratio is all more than 99%, catalytic decomposition temperature and corresponding resolving time relation are as shown in Figure 2, result shows within the scope of the catalytic temperature of 50 DEG C ~ 75 DEG C, and the catalytic decomposition efficiency of copper nickel compoilite oxide catalyst to clorox increases along with the rising of temperature; Be 8% liquor natrii hypochloritis for concentration, under 50 DEG C of catalytic temperatures, with the copper nickel compoilite oxide catalyst of solution 0.75% quality to be decomposed, 25 minutes can make the resolution ratio of clorox reach 99%; More than 70 DEG C under catalytic temperature, with the copper nickel compoilite oxide catalyst of solution 0.75% quality to be decomposed, 5 minutes can make the resolution ratio of clorox reach 99%.
Embodiment 5:
(1) configuration quality concentration is 8% liquor natrii hypochloritis 2000ml, measures 8% liquor natrii hypochloritis 6 parts of 300ml, it is put into respectively the beaker of 500ml and is placed in water bath with thermostatic control to be heated to temperature be 70 DEG C; Take respectively 0.25g, 0.5g, 0.75g, 1.0g, 1.25g, 1, the obtained copper nickel compoilite oxide catalyst of 5g embodiment 1 joins in each beaker, reacting under stirring condition to not having to stop during bubble formation, recording the reaction time under each catalyst amount.
(2) according to the content of clorox in solution after the method difference assaying reaction of GB19106-2003, calculate resolution ratio, in all reactant liquors, clorox resolution ratio is all more than 99%, as shown in Figure 3, result shows that the catalytic decomposition efficiency of copper nickel compoilite oxide catalyst to clorox increases along with the increase of consumption for the consumption of catalyst and the relation of time used; Be 8% liquor natrii hypochloritis for concentration, under 70 DEG C of catalytic temperatures, with the copper nickel compoilite oxide catalyst of solution 0.75% quality to be decomposed, 5 minutes can make the resolution ratio of clorox reach 99%; Catalyst amount is when being greater than 0.75%, and decomposition rate increases limited, and levels off to steadily, and consider practical application needs and cost, the catalyst amount with 0.75% is good.
Claims (1)
1. a preparation method for copper nickel oxide catalyst, is characterized in that, comprises the steps: 1) take the Ni (NO of 0.01mol
3)
26H
2cu (the NO of O and 0.01mol
3)
23H
2o, uses 100ml deionized water dissolving; 2) take the NaOH of 0.045mol, use 100ml deionized water dissolving; 3) NaOH solution is joined Ni (NO
3)
2with Cu (NO
3)
2mixed solution in, stirred at ambient temperature 8 hours, obtains precursor solution; 4) join in 250ml hydrothermal reaction kettle by described precursor solution, hydro-thermal reaction 10 hours at 140 DEG C, heating rate is 10 DEG C/min; 5) 4) reaction complete after, after question response liquid cools naturally, reactant is filtered; 6) filtrate use water is cleaned, after cleaning by products therefrom in drying box under 100 DEG C of conditions dry 8 hours, obtain copper nickel compoilite oxide catalyst.
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| CN106345485B (en) | 2016-08-25 | 2018-12-07 | 万华化学集团股份有限公司 | A kind of catalyst and its preparation method and application for catalytic oxidation treatment organic wastewater |
| CN108499566A (en) * | 2017-02-28 | 2018-09-07 | 中国科学院上海高等研究院 | A kind of preparation method and application of CuNi bases catalyst |
| WO2022183513A1 (en) * | 2021-03-05 | 2022-09-09 | 万华化学集团股份有限公司 | Catalytic dechlorination process for brackish water at outlet of electrolytic cell |
| CN115010286A (en) * | 2021-03-05 | 2022-09-06 | 万华化学集团股份有限公司 | Catalytic dechlorination process for dilute brine at outlet of electrolytic cell |
| CN113769757B (en) * | 2021-09-09 | 2023-06-16 | 武汉理工大学 | In-situ photothermal preparation of spinel structure Cu 1.5 Mn 1.5 O 4 Method for preparing catalyst and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039429A (en) * | 1989-12-08 | 1991-08-13 | Mineral Process Licensing Corp. B.V. | Hypochlorite removal from waste stream effluents |
| CN102626636A (en) * | 2012-03-22 | 2012-08-08 | 杭州中环化工设备有限公司 | Nanometer manganese dioxide-copper oxide composite catalyst and its application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5665633A (en) * | 1979-10-31 | 1981-06-03 | Chiba Enso Kagaku Kk | Hypochlorite decomposition catalyst |
-
2012
- 2012-11-12 CN CN201210463923.1A patent/CN103801297B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039429A (en) * | 1989-12-08 | 1991-08-13 | Mineral Process Licensing Corp. B.V. | Hypochlorite removal from waste stream effluents |
| CN102626636A (en) * | 2012-03-22 | 2012-08-08 | 杭州中环化工设备有限公司 | Nanometer manganese dioxide-copper oxide composite catalyst and its application |
Non-Patent Citations (1)
| Title |
|---|
| 《Manufacture characteristics of metal oxide–hydroxides for the catalytic decomposition of a sodium hypochlorite solution》;Kwang-Wook Kim et al;《Chemical Engineering Journal》;20120617;第200-202卷;第52-58页 * |
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