CN102659553A - Method for preparing organocopper bactericide from waste copper clad aluminum leads - Google Patents
Method for preparing organocopper bactericide from waste copper clad aluminum leads Download PDFInfo
- Publication number
- CN102659553A CN102659553A CN2012100900398A CN201210090039A CN102659553A CN 102659553 A CN102659553 A CN 102659553A CN 2012100900398 A CN2012100900398 A CN 2012100900398A CN 201210090039 A CN201210090039 A CN 201210090039A CN 102659553 A CN102659553 A CN 102659553A
- Authority
- CN
- China
- Prior art keywords
- copper
- solid
- liquid separation
- acid
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Apparatus For Disinfection Or Sterilisation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method for preparing an organocopper bactericide from waste copper clad aluminum leads. The method comprises the following steps of adding a hydrogen peroxide solution as an oxidant into waste copper clad aluminum leads so that copper of the surfaces of the waste copper clad aluminum leads is oxidized into cuprous oxide, and after cuprous oxide generation is finished, carrying out solid-liquid separation, 2, slowly adding an ammonia-water solution as a complexation agent into solid obtained by the solid-liquid separation so that cuprous oxide of the surfaces of the waste copper clad aluminum leads and ammonia water undergo a complexation reaction to produce an ammonia-copper complex, after ammonia-copper complex generation is finished, carrying out solid-liquid separation, and repeating the step 1 of oxidation and the step 2 of complexation, and 3, slowly adding an ammonia water-containing ammonia-copper complex solution obtained by the solid-liquid separation into a solution containing an organic acid so that the ammonia-copper complex and the organic acid undergo a ligand replacement reaction to produce an organic acid salt of copper. The method utilizes waste copper clad aluminum leads as raw materials to prepare the organocopper bactericide, changes waste into valuables, synchronously realizes waste utilization and ecological bactericide preparation and greatly reduces a production cost.
Description
Technical field
The present invention relates to a kind of preparation method of organic copper sterilant, be specifically related to a kind of method for preparing the organic copper sterilant with the copper cladding aluminum conductor waste material.
Background technology
Copper fungicide can be divided into inorganic copper fungicide and organic copper sterilant two big classes.In copper fungicide, inorganic copper fungicide often exists can not use, be easy to generate problems such as poisoning and residual quantity are big with other acid agrichemical.And compare with inorganic copper fungicide, it is neutral that organic copper sterilant great majority are, and affinity is better with being mixed property; Littler to the farm crop influence, " copper content " of preparation is lower, and be littler to the pollution of environment; Safety easy to use; Be convenient to operation, have on the multimass more, the technical and advantage used, receive day by day widely and paying attention to.
At present; All be to adopt mantoquita to prepare the organic copper sterilant in the industry; A kind of preparation method and application of copper rosinate are disclosed like Chinese patent document CN101935275A; The document adopts mantoquita and alkali lye reaction generation earlier verditer suspensoids such as copper sulfate, cupric chloride, cupric nitrate, neutralized verdigris, EDTA mantoquita, Cuprocitrol or ammoniacal copper complex ion, and then prepares copper rosinate with the sylvic acid solution reaction, produces exothermic phenomenon simultaneously.The method that the document adopts needs to generate earlier verditer, and cool off again and filters, the reaction process complicated operation, while solid-liquid phase reaction speed is slow, makes preparation cost higher.
Chinese patent document CN1264540 discloses a kind of preparation method of cupric oleate missible oil sterilant, after document employing oleic acid and sodium hydroxide mix and reacts, again with the mixed cupric oleate sterilant that gets of copper-bath.Chinese patent document CN1593154 discloses a kind of preparation method of copper humate sterilant, and it is copper-bath and humic acids to be mixed in pH is 8.5～10 scope make the copper humate sterilant.The method that these two pieces of documents adopt all is that the method through salt and salt or salt and acid-respons prepares the organic copper sterilant.
At present still do not have the report that utilizes metallic copper directly to prepare the organic copper sterilant, particularly utilize the part replacement(metathesis)reaction to prepare the report of organic copper sterilant.
Summary of the invention
The objective of the invention is to address the above problem, propose the method that a kind of production cost is lower, simple to operate, speed of response fast, reaction is prone to prepare with the copper cladding aluminum conductor waste material completely the organic copper sterilant.
The technical scheme that realizes the object of the invention is: a kind of method for preparing the organic copper sterilant with the copper cladding aluminum conductor waste material; Have following steps: 1. in the copper cladding aluminum conductor waste material, add hydrogen peroxide solution as oxygenant; Make the copper of copper cladding aluminum conductor scraped surface be oxidized to Red copper oxide, carry out solid-liquid separation during to regeneration Red copper oxide not; 2. 1. slowly add the ammonia soln as complexing agent in the solid that obtains of solid-liquid separation to step, making the Red copper oxide of copper cladding aluminum conductor scraped surface and ammoniacal liquor complexing is network ammonia copper, does not extremely carry out solid-liquid separation during regeneration network ammonia copper; 3. with step 2. the network ammonia copper solutions that contains ammoniacal liquor that obtains of solid-liquid separation slowly join and contain in the organic acid solution, make network ammonia copper and organic acid carry out the part replacement(metathesis)reaction and generate copper organic acid.
Above-mentioned steps also has before 3. 2. solid repeating step oxidation and the step complexing 2. 1. that obtain of solid-liquid separation of step; The oxygenant that oxidation is adopted is the liquid after the 1. middle solid-liquid separation of hydrogen peroxide solution or step; The complexing agent that complexing is adopted is the network ammonia copper solutions that contains ammoniacal liquor after the 2. middle solid-liquid separation of ammonia soln or step.
Said multiple number of times be 1 time or 2 times perhaps ... Perhaps N time; Be solid-liquid separation obtains after complexing solid number of times said N time for the metallic aluminium that do not contain any copper.
The described organic acid solution that contains is by organic acid and solvent composition; The weight ratio of said organic acid and solvent is 1: 1～1: 7.5; Described solvent is a kind of in methyl alcohol, ethanol, acetone, the turps or two kinds.
Network ammonia copper and the described organic acid weight ratio that contains in the organic acid solution in the said network ammonia copper solutions that contains ammoniacal liquor are 1: 4～1: 17.
Described organic acid is a kind of in sylvic acid, oleic acid, naphthenic acid or the humic acids.
The positively effect that the present invention has: it is feedstock production organic copper sterilant that (1) method of the present invention adopts the copper cladding aluminum conductor waste material, turns waste into wealth, and realizes " doulbe-sides' victory " of the preparation of utilization of waste material and ecological agricultural chemical, greatly reduces production cost.(2) the inorganic copper-based fungicide that obtains in the method for the present invention is the network ammonia copper solutions that contains ammoniacal liquor; This solution has germicidal action and Nutrition simultaneously, makes the organic copper-based fungicide lipid acid copper that obtains at last also have germicidal action and Nutrition simultaneously like this.(3) the present invention adopts the part replacement(metathesis)reaction that belongs to the reaction of liquid liquid interface to prepare the organic copper sterilant, and speed of response is fast like this, and is simple, easy to implement.(4) method of the present invention is simple to operate, and chemical reaction liquid can recycle, and has realized the zero release of waste liquid basically, is a very friendly process of environmental protection.
Embodiment
(embodiment 1)
Present embodiment is for being prepared the method for copper rosinate by the copper cladding aluminum conductor waste material.
Wherein the copper cladding aluminum conductor waste material is to pulverize the about 1mm of 3.5g diameter that the insulation paint film remove the parcel lead obtains, the copper cladding aluminum conductor waste material in small, broken bits of the about 2mm～3mm of length through mechanical means, and wherein copper accounts for 1/3 of gross weight.
The preparation method has following steps:
1. above-mentioned copper cladding aluminum conductor waste material in small, broken bits is put into beaker, adding concentration is the hydrogen peroxide solution of 15wt%, makes the copper of copper cladding aluminum conductor scraped surface in small, broken bits be oxidized to red Red copper oxide, carries out solid-liquid separation during to the red Red copper oxide of regeneration not.
2. with step 1. the solid that obtains of solid-liquid separation put into beaker; Slowly adding concentration is the ammonia soln of 25wt%; Making the Red copper oxide and the ammoniacal liquor complexing of copper cladding aluminum conductor scraped surface in small, broken bits is network ammonia copper; This moment, solution gradually became blue, when solution colour no longer changes (promptly not regeneration network ammonia copper), carried out solid-liquid separation.Obtain the network ammonia copper solutions that 10.0g contains ammoniacal liquor, network ammonia copper concentration is 1.2wt%.
3. with step 2. the network ammonia copper solutions that contains ammoniacal liquor that obtains of solid-liquid separation slowly be added drop-wise in the solution that contains sylvic acid and (also can the solution that contain sylvic acid be slowly joined in this network ammonia copper solutions that contains ammoniacal liquor); Make the reaction of network ammonia copper and sylvic acid generate copper rosinate; Dropping process color becomes green by blueness, and produces demixing phenomenon.This solution that contains sylvic acid is to be mixed by the sylvic acid of 2.0g and the turps of 15.0g, and its concentration is 11.8wt%.
After reacting completely, use the water trap separating and dehydrating, obtaining 17.0g concentration is the copper rosinate solution of 3.5wt%.
(embodiment 2)
Present embodiment and embodiment 1 are basic identical, and difference is: step also has that 2. oxidation and the step complexing 2. 1. of the solid repeating step that obtains of solid-liquid separation be once to step before 3.; The oxygenant that oxidation is adopted is the liquid after the 1. middle solid-liquid separation of step; The complexing agent that complexing is adopted is the network ammonia copper solutions that contains ammoniacal liquor after the 2. middle solid-liquid separation of step.The network ammonia copper solutions that contains ammoniacal liquor that obtains of the 2. final solid-liquid separation of step is 10.2g like this, and network ammonia copper concentration is 2.3wt%.The weight of the copper rosinate solution that finally obtains is 17.1g, and concentration is 6.9wt%.
(embodiment 3)
Present embodiment and embodiment 1 are basic identical, and difference is: step also has before 3. the 2. solid repeating step that obtains of solid-liquid separation oxidation and step complexing 2. 1. three times of step; The oxygenant that oxidation is adopted is the liquid after the 1. middle solid-liquid separation of step; The complexing agent that complexing is adopted is the network ammonia copper solutions that contains ammoniacal liquor after the 2. middle solid-liquid separation of step.The network ammonia copper solutions that contains ammoniacal liquor that obtains of the 2. final solid-liquid separation of step is 10.3g like this, and network ammonia copper concentration is 3.4wt%.The weight of the copper rosinate solution that finally obtains is 17.2g, and concentration is 10.3wt%.
(embodiment 4)
Present embodiment and embodiment 1 are basic identical; Difference is: step also has before 3. 2. solid repeating step oxidation and the step complexing 2. 1. that obtain of solid-liquid separation of step, and the solid that obtains until the 2. final solid-liquid separation of step is the metallic aluminium that does not contain any copper.
Wherein the oxygenant that adopts of oxidation is the 1. liquid that obtains of solid-liquid separation of step; When oxygenant being joined oxidation solid wire waste material in the beaker; The solid wire scraped surface is not during the red Red copper oxide of regeneration; The a spot of hydrogen peroxide solution of restock if still do not generate red Red copper oxide, explains that then this solid wire waste material has been the metallic aluminium that does not contain any copper.
Wherein the complexing agent that adopts of complexing is the 2. liquid that obtains of solid-liquid separation of step, every complexing once, the color relation of solution is deepened once; When the color of solution is no longer deepened when complexing; The a spot of ammonia soln of restock, if solution is still no longer deepened, then oxygen-freeization is cuprous for the lead waste material.
The 2. final solid-liquid separation of step obtains the network ammonia copper solutions that 2.3g solid metal aluminium and 15.7g contain ammoniacal liquor like this, and wherein the concentration of network ammonia copper is 15wt%.
3. step is: with step 2. the network ammonia copper solutions that contains ammoniacal liquor that obtains of solid-liquid separation slowly be added drop-wise in the solution that contains sylvic acid and (also can the solution that contain sylvic acid be slowly joined in this network ammonia copper solutions that contains ammoniacal liquor); Make the reaction of network ammonia copper and sylvic acid generate copper rosinate; Dropping process color becomes green by blueness, and produces demixing phenomenon.This solution that contains sylvic acid is to be mixed by the sylvic acid of 10.0g and the turps of 43.0g, and its concentration is 18.9%.
After reacting completely, use the water trap separating and dehydrating, obtaining 54.0g concentration is the copper rosinate solution of 20.4wt%.
(embodiment 5～embodiment 8)
Each embodiment and embodiment 4 are basic identical, and difference is seen table 1.
Table 1
| ? | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Sylvic acid | 10.0g | 10.0g | 20.0g | 10.0g | 20.0g |
| Solvent | 43.0g turps | 8.0g turps and the ethanol of 8.0g | 32.0g ethanol | 15.0g turps and the ethanol of 5.0g | 5.0g turps and the ethanol of 15.0g |
| Copper rosinate weight | 54.0g | 27.0g | 53.1g | 31.0g | 41.1g |
| Copper rosinate concentration | 20.4wt% | 40.7wt% | 22.2wt% | 35.5wt% | 28.7wt% |
(embodiment 9～embodiment 11)
The preparation method of each embodiment and embodiment 4 are basic identical, and difference is being seen table 2.
Table 2
| ? | Embodiment 4 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Contain organic acid solution | 10.0g sylvic acid and the turps of 43.0g | 10.0g naphthenic acid and the turps of 43.0g | 10.0g oleic acid and the ethanol of 32.0g | 10.0g humic acids and the ethanol of 32.0g |
| Organic acid concentration | 18.9wt% | 18.9wt% | 23.8wt% | 23.8wt% |
| Part replacement(metathesis)reaction colour-change | Blueness becomes green | Blueness becomes deep green | Blueness becomes blue-greenish colour | Blueness becomes brown |
| Copper organic acid | Copper rosinate | Copper naphthenate | Cupric oleate | Copper humate |
| Copper organic acid weight | 54.0g | 54.1g | 43.1g | 42.4g |
| Copper organic acid concentration | 20.4wt% | 10.5wt% | 25.7wt% | 24.5wt% |
Claims (10)
1. one kind prepares the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that having following steps:
1. in the copper cladding aluminum conductor waste material, add hydrogen peroxide solution, make the copper of copper cladding aluminum conductor scraped surface be oxidized to Red copper oxide, carry out solid-liquid separation during to regeneration Red copper oxide not as oxygenant;
2. 1. slowly add the ammonia soln as complexing agent in the solid that obtains of solid-liquid separation to step, making the Red copper oxide of copper cladding aluminum conductor scraped surface and ammoniacal liquor complexing is network ammonia copper, does not extremely carry out solid-liquid separation during regeneration network ammonia copper;
3. with step 2. the network ammonia copper solutions that contains ammoniacal liquor that obtains of solid-liquid separation slowly join and contain in the organic acid solution, make network ammonia copper and organic acid carry out the part replacement(metathesis)reaction and generate copper organic acid.
2. according to claim 1ly prepare the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that: step also has before 3. 2. solid repeating step oxidation and the step complexing 2. 1. that obtain of solid-liquid separation of step; The oxygenant that oxidation is adopted is the liquid after the 1. middle solid-liquid separation of hydrogen peroxide solution or step; The complexing agent that complexing is adopted is the network ammonia copper solutions that contains ammoniacal liquor after the 2. middle solid-liquid separation of ammonia soln or step.
3. according to claim 2ly prepare the method for organic copper sterilant, it is characterized in that with the copper cladding aluminum conductor waste material: said multiple number of times be 1 time or 2 times perhaps ... Perhaps N time; Be solid-liquid separation obtains after complexing solid number of times said N time for the metallic aluminium that do not contain any copper.
4. prepare the method for organic copper sterilant according to one of claim 1 to 3 is described with the copper cladding aluminum conductor waste material, it is characterized in that: the described organic acid solution that contains is by organic acid and solvent composition; The weight ratio of said organic acid and solvent is 1: 1～1: 7.5; Described solvent is a kind of in methyl alcohol, ethanol, acetone, the turps or two kinds.
5. prepare the method for organic copper sterilant according to one of claim 1 to 3 is described with the copper cladding aluminum conductor waste material, it is characterized in that: network ammonia copper and the described organic acid weight ratio that contains in the organic acid solution in the said network ammonia copper solutions that contains ammoniacal liquor are 1: 4～1: 17.
6. according to claim 4ly prepare the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that: network ammonia copper and the described organic acid weight ratio that contains in the organic acid solution in the said network ammonia copper solutions that contains ammoniacal liquor are 1: 4～1: 17.
7. prepare the method for organic copper sterilant according to one of claim 1 to 3 is described with the copper cladding aluminum conductor waste material, it is characterized in that: described organic acid is a kind of in sylvic acid, oleic acid, naphthenic acid or the humic acids.
8. according to claim 4ly prepare the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that: described organic acid is a kind of in sylvic acid, oleic acid, naphthenic acid or the humic acids.
9. according to claim 5ly prepare the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that: described organic acid is a kind of in sylvic acid, oleic acid, naphthenic acid or the humic acids.
10. according to claim 6ly prepare the method for organic copper sterilant with the copper cladding aluminum conductor waste material, it is characterized in that: described organic acid is a kind of in sylvic acid, oleic acid, naphthenic acid or the humic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210090039.8A CN102659553B (en) | 2012-03-30 | 2012-03-30 | Method for preparing organocopper bactericide from waste copper clad aluminum leads |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210090039.8A CN102659553B (en) | 2012-03-30 | 2012-03-30 | Method for preparing organocopper bactericide from waste copper clad aluminum leads |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659553A true CN102659553A (en) | 2012-09-12 |
| CN102659553B CN102659553B (en) | 2014-10-22 |
Family
ID=46769166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210090039.8A Expired - Fee Related CN102659553B (en) | 2012-03-30 | 2012-03-30 | Method for preparing organocopper bactericide from waste copper clad aluminum leads |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659553B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106538523A (en) * | 2016-11-02 | 2017-03-29 | 常州工学院 | Compound wire waste recovery is utilized and prepares copper agent suspension sterilization and disinsection agent method |
| CN110759426A (en) * | 2019-11-15 | 2020-02-07 | 江苏理工学院 | Super-hydrophobic copper mesh and simple preparation method and application thereof |
| WO2020170011A1 (en) * | 2019-02-19 | 2020-08-27 | Upl Ltd | Process for preparation of copper compounds |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775097A (en) * | 1971-04-15 | 1973-11-27 | Copper Range Co | Method of extracting a metal from a material containing the metal in elemental form |
| WO1991001942A1 (en) * | 1989-08-01 | 1991-02-21 | Australian Copper Company Pty. Ltd. | Production of copper compounds |
| US5366599A (en) * | 1992-03-30 | 1994-11-22 | Dowa Iron Powder Co., Ltd. | Method of selective recovery of ferrous and nonferrous metals from industrial wastes and scrap home electric appliances |
| JPH07224334A (en) * | 1993-12-16 | 1995-08-22 | Sangyo Souzou Kenkyusho | Separating and recovering method of copper |
| CN101560605A (en) * | 2009-06-04 | 2009-10-21 | 常州工学院 | Method for separating copper and aluminium from copper-cladding aluminium waste leading wire |
| CN101935275A (en) * | 2009-06-29 | 2011-01-05 | 孔波 | Preparation method and application of gum rosin acid copper |
| CN102181644A (en) * | 2011-04-13 | 2011-09-14 | 深圳市格林美高新技术股份有限公司 | Method for reclaiming rare noble metals from waste circuit board |
| CN102634664A (en) * | 2012-03-30 | 2012-08-15 | 常州工学院 | Treatment method of copper clad aluminum lead wire wastes |
-
2012
- 2012-03-30 CN CN201210090039.8A patent/CN102659553B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775097A (en) * | 1971-04-15 | 1973-11-27 | Copper Range Co | Method of extracting a metal from a material containing the metal in elemental form |
| WO1991001942A1 (en) * | 1989-08-01 | 1991-02-21 | Australian Copper Company Pty. Ltd. | Production of copper compounds |
| US5366599A (en) * | 1992-03-30 | 1994-11-22 | Dowa Iron Powder Co., Ltd. | Method of selective recovery of ferrous and nonferrous metals from industrial wastes and scrap home electric appliances |
| JPH07224334A (en) * | 1993-12-16 | 1995-08-22 | Sangyo Souzou Kenkyusho | Separating and recovering method of copper |
| CN101560605A (en) * | 2009-06-04 | 2009-10-21 | 常州工学院 | Method for separating copper and aluminium from copper-cladding aluminium waste leading wire |
| CN101935275A (en) * | 2009-06-29 | 2011-01-05 | 孔波 | Preparation method and application of gum rosin acid copper |
| CN102181644A (en) * | 2011-04-13 | 2011-09-14 | 深圳市格林美高新技术股份有限公司 | Method for reclaiming rare noble metals from waste circuit board |
| CN102634664A (en) * | 2012-03-30 | 2012-08-15 | 常州工学院 | Treatment method of copper clad aluminum lead wire wastes |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106538523A (en) * | 2016-11-02 | 2017-03-29 | 常州工学院 | Compound wire waste recovery is utilized and prepares copper agent suspension sterilization and disinsection agent method |
| WO2020170011A1 (en) * | 2019-02-19 | 2020-08-27 | Upl Ltd | Process for preparation of copper compounds |
| CN110759426A (en) * | 2019-11-15 | 2020-02-07 | 江苏理工学院 | Super-hydrophobic copper mesh and simple preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659553B (en) | 2014-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yi et al. | Epigallocatechin-3-gallate-coated Fe3O4 as a novel heterogeneous catalyst of peroxymonosulfate for diuron degradation: performance and mechanism | |
| CN102659553B (en) | Method for preparing organocopper bactericide from waste copper clad aluminum leads | |
| CN102935513A (en) | Stable nanometer silver colloidal sol and preparation method thereof | |
| CN106630103A (en) | Method for degrading phenol by solid catalyst | |
| CN103012109B (en) | Preparation method for metal oleate | |
| Maham et al. | Biosynthesis of the CuO nanoparticles using Euphorbia Chamaesyce leaf extract and investigation of their catalytic activity for the reduction of 4‐nitrophenol | |
| CN102354571A (en) | Nano-copper conductive slurry preparation method by utilizing printed circuit board alkaline etching waste liquid | |
| CN103232055A (en) | Method of preparing basic copper carbonate | |
| CN102671706A (en) | Efficient Fenton-like system catalyst and preparation method thereof | |
| CN103993322A (en) | Preparation method of copper corrosion inhibitor | |
| Halim et al. | Parametric studies of Cu (II) ion extraction into palm kernel fatty acid distillate as a green organic solvent | |
| CN101611719B (en) | Plant growth accelerant and preparation method thereof | |
| CN100589904C (en) | Preparation of nano copper particle | |
| CN113354024A (en) | Method for preparing nickel nitrate by using electroplating wastewater | |
| CN102424500B (en) | Recycling method for zero discharge of garbage leachate and domestic sewage | |
| CN102107960A (en) | Method for processing high-arsenic and high-alkali wastewater | |
| CN101966595A (en) | Nano silver preparation process | |
| CN102634664B (en) | Treatment method of copper clad aluminum lead wire wastes | |
| CN101386910A (en) | Copper extractive agent | |
| CN107442146A (en) | Silver orthophosphate/silver bromide hetero-junctions nano particle, preparation method and applications | |
| CN105315770A (en) | High-temperature-sintered environment-friendly type water-soluble automotive glass varnish and preparation method | |
| CN101607872A (en) | The preparation method of spectrophotometricalpure pure petroleum ether | |
| CN103785849A (en) | Preparation method of TH-908 dispersed iron nano-particles | |
| Akhmadullina et al. | Unexpected participation of nucleophiles in the reaction of palladium (II) acetate with divalent 3 d metals | |
| CN105540923A (en) | Method for removing 2-mercaptopyridine-N-oxide in wastewater and recycling of 2-mercaptopyridine-N-oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141022 Termination date: 20170330 |