CN101195497A - Process for producing cupric hydroxide or cupric oxide - Google Patents
Process for producing cupric hydroxide or cupric oxide Download PDFInfo
- Publication number
- CN101195497A CN101195497A CNA2006101190456A CN200610119045A CN101195497A CN 101195497 A CN101195497 A CN 101195497A CN A2006101190456 A CNA2006101190456 A CN A2006101190456A CN 200610119045 A CN200610119045 A CN 200610119045A CN 101195497 A CN101195497 A CN 101195497A
- Authority
- CN
- China
- Prior art keywords
- copper
- basic
- hydroxide
- cupric
- chloride
- 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.)
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims abstract description 38
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229960004643 cupric oxide Drugs 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 36
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 36
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 28
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 229960003280 cupric chloride Drugs 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims 2
- 239000013067 intermediate product Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- -1 ammonium ions Chemical class 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- AWZACWPILWGEQL-UHFFFAOYSA-M azanium;copper(1+);sulfate Chemical compound [NH4+].[Cu+].[O-]S([O-])(=O)=O AWZACWPILWGEQL-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XCBKGJWOCHSAMS-UHFFFAOYSA-L copper;dichlorocopper Chemical compound [Cu].Cl[Cu]Cl XCBKGJWOCHSAMS-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a process for preparing copper hydroxide or copper oxide. Soluble cupriferous ions (cupric nitrate, copper chloride and copper sulphate) generated in the production of wiring boards are taken as raw materials to be synthesized with ammonium ions of basic copper chloride or sodium hydroxide to generate basic copper salt (basic copper nitrate, basic copper sulphate and basic copper chloride), furthermore, products of basic copper salt reacts with the sodium hydroxide to generate copper hydroxide or copper oxide, and glycerin as stabilizing agent is added in. .The process of preparation has the advantages of stable products, easy washing, high purity, easy raw material achievement, high absorption rate and little environmental pollution.
Description
Technical field
The present invention relates to the preparation method of a kind of copper hydroxide or cupric oxide.
Background technology
Copper hydroxide is a kind of important catalyst, industrial chemicals and pesticide material, and the synthetic method of copper hydroxide mainly is by two kinds at present: first kind is to generate copper hydroxide when becoming copper sulfate ammonium ion repeated hydrogenation sodium oxide with copper sulfate and ammonia synthesis.This technology cost height, excess of ammonia and cuprammonium ionic soil are heavy, and productive rate is low, the present domestic scale operation that do not form.Second kind is to carry out the neutralization reaction generation with solubility chlorination cupric ion that produces in the circuit board industrial and alkaline cupric chloride ammonium ion to contain a large amount of copper hydroxide products based on basic copper chloride, can't generate purer copper hydroxide, the product that in fact this technology the produce copper hydroxide of to say so, can only think to contain the basic copper chloride copper sludge of copper hydroxide, the product of this method production can not use as copper hydroxide at present, but is used to produce the basic material and the copper smelting industry of Chemicals such as cuprous chloride as copper-containing raw material.
At present the main application of copper hydroxide product is agricultural chemicals and mantoquita Chemical market, and this market demand purity is greater than 98% copper hydroxide, and fineness can effectively be controlled to reach and is difficult for precipitation.Because production technology does not reach the purity of market demand, so the content among the Q/HG22-2032-82 of domestic standard Shanghai can only be decided to be 95%, can't formulate content greater than 98% in the past, so can't satisfy market demand, we have carried out big quantity research for this reason.
Summary of the invention
Studies show that, adopting synthetic copper hydroxide of branch two step method or cupric oxide mainly is that the first step reaction is the solubility cupric nitrate that produces during wiring board is produced, the copper ions of cupric chloride and copper sulfate and solubility chlorination cuprammonium ion or sodium hydroxide reaction generate insoluble basic copper nitrate, Basic Chrome Sulphate and basic copper chloride, just be easy to solubility chlorination ammonium or the sodium chloride solution of reaction by-product separated through centrifugal or press filtration this moment, again will be through the basic copper nitrate after the washing, Basic Chrome Sulphate and basic copper chloride and aqueous sodium hydroxide solution reaction generate copper hydroxide or cupric oxide, in the slurry of moisture copper hydroxide, add glycerine as stablizer, after air stream drying or drying room drying, be finished product.
Separate through mother liquor owing to having produced side product sodium chloride after synthetic in the above-mentioned reaction, avoided the side reaction of generation when back road alkali type nantokite and sodium hydroxide reaction, be that ammonium chloride and sodium hydroxide can generate sodium-chlor and ammonia, cause ammonia to pollute and consume sodium hydroxide, simultaneously excessive sodium-chlor and ammonium chloride can be adsorbed on the copper hydroxide and cause the content of copper hydroxide on the low side and to produce color be abnormal grey black.
Description of drawings
Fig. 1 is preparation method's process flow sheet of copper hydroxide of the present invention or cupric oxide.
Embodiment
Below in conjunction with specific embodiment copper hydroxide preparation method of the present invention is described in further detail.
As shown in Figure 1, to be that 1～30% solution is placed in the container 1 after filtration by the solubility cupric of the cupric nitrate that produces in the wiring board production, copper sulfate or cupric chloride, be 1～30% alkaline cupric chloride cuprammonium ion with cupric or be that 1～45% sodium hydroxide solution is placed in the container 2 after filtering, in reactor 4, the solution in two containers is added under stirring state simultaneously
When the PH in the molten device be controlled at 4.5～9 and liquor capacity in reactor 4 rise to 2000L and begin to open reactor 4 end opening baiting valves in charging reaction limit, limit when above, open that the press filtration pump carries out press filtration or whizzer is centrifugal, be washed with water to PH6～8, unload basic copper nitrate or Basic Chrome Sulphate or basic copper chloride and place it in and add water in the reactor 5 earlier to break into pulpous state stand-by.Adding sodium hydroxide and water in container 3, to be made into content be 1～45% aqueous sodium hydroxide solution, add in the reactor 5 then while stirring, the total amount that adds sodium hydroxide be copper hydroxide 20% in, the content of sodium hydroxide is controlled in 20% in the aqueous solution.The reinforced restir 2 hours of finishing, add glycerine this moment in reactor 5, add-on is 0～20% of a copper hydroxide total amount, open reactor 5 end opening baiting valves this moment, open that press filtration pump 6 carries out press filtration or whizzer is centrifugal, the aqueous solution that preparation contains 0～10% glycerine in reactor 5 is used to wash to PH6～8, unloads the copper hydroxide wet feed, in air stream drying or drying room 7, carry out the dry hydrogen cupric oxide, analyze qualified back packing warehouse-in then.
Claims (6)
1. the preparation method of copper hydroxide or cupric oxide, by the solubility cupric of the cupric nitrate that produces in the wiring board production, copper sulfate or cupric chloride is that the sodium hydroxide solution that 1～30% solution and cupric are 1～30% alkaline cupric chloride cuprammonium ion or 1～45% reacts at aqueous phase, makes basic copper nitrate, Basic Chrome Sulphate or basic copper chloride product; Basic copper nitrate, Basic Chrome Sulphate or basic copper chloride product after by-product solubility chlorination ammonium or the sodium-chlor separation are reacted with sodium hydroxide again, make copper hydroxide or cupric oxide; Add glycerine as stablizer in washing water or wet copper hydroxide, add-on is 0～20% of a copper hydroxide amount, makes stable form high purity content after drying greater than 98% copper hydroxide.
2. the preparation method of copper hydroxide as claimed in claim 1 is characterized in that: describedly reacted at aqueous phase by soluble copper salts such as cupric nitrate, copper sulfate and cupric chloride and alkaline cupric chloride ammonium ion or sodium hydroxide.
3. the preparation method of copper hydroxide as claimed in claim 1, it is characterized in that: the intermediate product that described reaction obtains is alkali type nantokites such as basic copper nitrate, basic copper chloride, Basic Chrome Sulphate.
4. the preparation method of copper hydroxide as claimed in claim 1 is characterized in that: described reaction generates alkali type nantokites such as water-fast basic copper nitrate, basic copper chloride, Basic Chrome Sulphate and separates with reaction by-product salt.
5. the preparation method of copper hydroxide as claimed in claim 1 or cupric oxide is characterized in that: described basic copper nitrate, basic copper chloride, Basic Chrome Sulphate and aqueous sodium hydroxide solution reaction generate copper hydroxide or cupric oxide.
6. the preparation method of copper hydroxide as claimed in claim 1 is characterized in that: described product copper hydroxide adds glycerine as stablizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610119045A CN101195497B (en) | 2006-12-04 | 2006-12-04 | Process for producing cupric hydroxide or cupric oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610119045A CN101195497B (en) | 2006-12-04 | 2006-12-04 | Process for producing cupric hydroxide or cupric oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101195497A true CN101195497A (en) | 2008-06-11 |
| CN101195497B CN101195497B (en) | 2012-10-03 |
Family
ID=39546156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610119045A Active CN101195497B (en) | 2006-12-04 | 2006-12-04 | Process for producing cupric hydroxide or cupric oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101195497B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633290A (en) * | 2012-03-26 | 2012-08-15 | 廖勇志 | Preparation method for basic copper nitrate |
| CN103011253A (en) * | 2012-12-21 | 2013-04-03 | 嘉兴德达资源循环利用有限公司 | Method for preparing copper hydroxide with copper ammonia etching waste liquid |
| CN103466683A (en) * | 2013-09-12 | 2013-12-25 | 昆山德阳新材料科技有限公司 | Preparation method of high-purity electroplating-grade copper oxide |
| CN103739000A (en) * | 2013-12-25 | 2014-04-23 | 广州科城环保科技有限公司 | Production method of high-purity electroplating grade copper oxide |
| CN104297415A (en) * | 2014-10-27 | 2015-01-21 | 扬州协鑫光伏科技有限公司 | Detection method for glycerin content in cutting fluid |
| CN106673048A (en) * | 2017-03-24 | 2017-05-17 | 东莞市广华化工有限公司 | A kind of basic copper chloride conversion basic copper carbonate method |
| CN107381746A (en) * | 2017-08-23 | 2017-11-24 | 华南理工大学 | A kind of method for being removed in waste water and reclaiming copper |
| CN109845759A (en) * | 2019-03-15 | 2019-06-07 | 威海市农业科学院 | A kind of Bordeaux mixture and preparation method, application method of improvement |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
| CN114959732A (en) * | 2022-06-15 | 2022-08-30 | 昆明理工大学 | Preparation method and purification process of copper hydroxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047069A (en) * | 1989-05-12 | 1990-11-21 | 叶远安 | Alikali cupric carbonate produced by boiling water |
| CN1082004A (en) * | 1992-08-12 | 1994-02-16 | 黄石市能源综合科学技术研究所 | Produce a kind of efficient process of ventilation breather or cupric oxide |
| CN1172074A (en) * | 1997-08-15 | 1998-02-04 | 张礼英 | Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion |
-
2006
- 2006-12-04 CN CN200610119045A patent/CN101195497B/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633290A (en) * | 2012-03-26 | 2012-08-15 | 廖勇志 | Preparation method for basic copper nitrate |
| CN103011253A (en) * | 2012-12-21 | 2013-04-03 | 嘉兴德达资源循环利用有限公司 | Method for preparing copper hydroxide with copper ammonia etching waste liquid |
| CN103466683B (en) * | 2013-09-12 | 2015-11-25 | 昆山德阳新材料科技有限公司 | A kind of preparation method of high-purity electroplating-gradecopper copper oxide |
| CN103466683A (en) * | 2013-09-12 | 2013-12-25 | 昆山德阳新材料科技有限公司 | Preparation method of high-purity electroplating-grade copper oxide |
| CN103739000A (en) * | 2013-12-25 | 2014-04-23 | 广州科城环保科技有限公司 | Production method of high-purity electroplating grade copper oxide |
| CN103739000B (en) * | 2013-12-25 | 2015-11-18 | 广州科城环保科技有限公司 | A kind of production method of high-purity plating-grade copper oxide |
| CN104297415A (en) * | 2014-10-27 | 2015-01-21 | 扬州协鑫光伏科技有限公司 | Detection method for glycerin content in cutting fluid |
| CN104297415B (en) * | 2014-10-27 | 2016-08-24 | 扬州协鑫光伏科技有限公司 | The detection method of glycerin components in cutting liquid |
| CN106673048A (en) * | 2017-03-24 | 2017-05-17 | 东莞市广华化工有限公司 | A kind of basic copper chloride conversion basic copper carbonate method |
| CN107381746A (en) * | 2017-08-23 | 2017-11-24 | 华南理工大学 | A kind of method for being removed in waste water and reclaiming copper |
| CN109845759A (en) * | 2019-03-15 | 2019-06-07 | 威海市农业科学院 | A kind of Bordeaux mixture and preparation method, application method of improvement |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
| CN114516654B (en) * | 2022-02-09 | 2024-02-27 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by preparation method |
| CN114959732A (en) * | 2022-06-15 | 2022-08-30 | 昆明理工大学 | Preparation method and purification process of copper hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101195497B (en) | 2012-10-03 |
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