CN106698577A - Novel method for treating copper ammonia waste etching liquid - Google Patents
Novel method for treating copper ammonia waste etching liquid Download PDFInfo
- Publication number
- CN106698577A CN106698577A CN201510769303.4A CN201510769303A CN106698577A CN 106698577 A CN106698577 A CN 106698577A CN 201510769303 A CN201510769303 A CN 201510769303A CN 106698577 A CN106698577 A CN 106698577A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- adsorption
- new method
- cuprammonium
- absorption
- 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.)
- Withdrawn
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 title claims abstract description 17
- 238000005530 etching Methods 0.000 title claims abstract description 9
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 title abstract 3
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000003463 adsorbent Substances 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000011069 regeneration method Methods 0.000 claims abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- -1 copper ammonia ions Chemical class 0.000 abstract 2
- 238000005406 washing Methods 0.000 description 5
- 239000006210 lotion Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a novel method for treating copper ammonia waste etching liquid. The method is mainly characterized in that copper ammonia ions in a copper ammonia waste liquid are adsorbed by an adsorbent, so that copper ions in the liquid after adsorption can be reduced to 0.3 mg/L or lower, and the pH can be reduced to about 7.0. After adsorption saturation of the adsorbent, regeneration can be realized by acid, and repeated utilization can be realized. The method is easy to operate, and the cost is low; the adsorbent not only has high adsorption capacity to copper ammonia ions, but also has high adsorption capacity to metal ions such as nickel, cobalt and chromium and many kinds of organic substances.
Description
Technical field
The present invention is a kind of new method of cuprammonium etching waste liquor treatment, specifically using the method for the cuprammonium ion in a kind of adsorbent absorption cuprammonium waste liquid etc..
Background technology
In cuprammonium etching industry, a large amount of cuprammonium etching waste liquors can be produced.Most copper ammoniacal etchant waste liquid can be able to by reuse by regeneration techniques.But in production process, still there are many cuprammonium washing lotions to need to be processed into sewage disposal system.Prior art typically uses chemical precipitation method or absorption method etc. for the treatment of this heavy metal ion waste liquid.Such as the cuprammonium waste liquid of above-mentioned low concentration, prior art carries out chemical precipitation using ferrous sulfate, not only relatively costly, and can produce a large amount of solid slags, and copper ion therein etc. is also difficult to reclaim.By absorption method, such as cocoanut active charcoal, general charcoal absorption is generally physical absorption, and the adsorption effect of heavy metal ion is general, and this kind of activated carbon is relatively costly.
And passing through lignite or weathered coal is adsorbed, it is loose structure, and containing a large amount of humic acid, does not only have very strong physical absorption ability, also there is chemical adsorption capacity.This method not only low cost, and have very strong adsorption capacity to all kinds of heavy metal ion and gas chromatography, can also by after pyrolysis its metal concentrate be reclaimed.
The content of the invention
The present invention is intended to provide a kind of process is simple, low cost, and can circulation and stress cuprammonium liquid waste processing method.
Specifically, after cuprammonium waste liquid is adsorbed by the adsorption column equipped with adsorbent, the adsorbed agent of cuprammonium ion in cuprammonium waste liquid is adsorbed.And by after absorption, below 0.3mg/L being down to from the copper ion in liquid after the absorption of adsorption column outflow, pH can be down to 7.0 or so, can be to system reuse.And after adsorbent adsorption saturation, the adsorbance of its copper is up to 8%-12%（Mass fraction）.
In technique of the present invention, its adsorbent is lignite or weathered coal, can be crushed to particle diameter for 1-2mm is advisable.And after alkalization can be soaked with alkali such as NaOH, the adsorption effect of adsorbent can be improved.
In technique of the present invention, its adsorption process also can carry out vibration absorption with adsorbent and feed liquid.
In technique of the present invention, after adsorbent adsorption saturation, can be by with the acid backwash and regeneration such as hydrochloric acid or sulfuric acid, repeated multiple times can use.
In technique of the present invention, after adsorbent adsorption saturation, after saturation adsorbent is pyrolyzed, oxidation copper concentrate of the cupric more than 30% can be obtained.
And adsorbent of the present invention not only has very strong adsorption capacity to cuprammonium ion, and also there is stronger absorption to the metal ions such as nickel, cobalt, chromium and many type organics.Heavy metal ion adsorbed, dyeing waste water decolouring of cobalt, nickel such as in EDAT waste liquids etc..And for different solutions type, the optimal adsorption pH of its absorption stoste would also vary from.
Brief description of the drawings
Fig. 1 is process flow diagram of the invention.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, and protection scope of the present invention includes but is not limited to following examples.
Cupric is 5.4g/L in the cuprammonium washing lotion of certain circuit board factory, by it by equipped with the adsorption column that particle diameter is 1-2mm adsorbents, entering flow quantity for 100mL/min.And the internal diameter of adsorption column is 5cm, wherein equipped with adsorbent 50cm high.By being water white transparency liquid from liquid after the absorption of adsorption column outflow after absorption, its copper ion is 0.3mg/L.Liquid carries out board-washing and uses when washing lotion is back to etching machine after this absorption, and washing lotion can be made to reach zero-emission.
After adsorbent saturation, the copper chloride and ammonium chloride backwash liquor of high concentration are obtained with high concentrated acid backwash adsorbent, this backwash liquor is returned prepares cuprammonium etching solution.
Claims (8)
1. the new method that a kind of cuprammonium etching waste liquor is processed, after cuprammonium waste liquid is adsorbed by the adsorption column equipped with adsorbent, the adsorbed agent of cuprammonium ion in cuprammonium waste liquid is adsorbed；And by after absorption, below 0.3mg/L being down to from the copper ion in liquid after the absorption of adsorption column outflow, pH can be down to 7.0 or so, can be to system reuse；And after adsorbent adsorption saturation, the adsorbance of its copper is up to 8%-12%（Mass fraction）.
2. new method according to claim 1, it is characterised in that the adsorbent is lignite or weathered coal.
3. the new method according to claim 1 and 2, it is characterised in that after this adsorbent can soak alkalization with alkali such as NaOH, the adsorption effect of adsorbent can be improved.
4. the new method according to claim 1 and 2, it is characterised in that adsorption process also can carry out vibration absorption with adsorbent and feed liquid.
5. the new method according to claim 1 and 2, it is characterised in that after this adsorbent adsorption saturation, can be by with the acid backwash and regeneration such as hydrochloric acid or sulfuric acid, repeated multiple times can use.
6. the new method according to claim 1 and 2, it is characterised in that after this adsorbent adsorption saturation, after saturation adsorbent is pyrolyzed, can obtain oxidation copper concentrate of the cupric more than 30%.
7. the new method according to claim 1 and 2, it is characterised in that the adsorbent not only has very strong adsorption capacity to cuprammonium ion, and also has stronger absorption to the metal ions such as nickel, cobalt, chromium and many type organics；Heavy metal ion adsorbed, dyeing waste water decolouring of cobalt, nickel such as in EDAT waste liquids etc..
8. the new method according to claim 1,2 and 7, it is characterised in that optimal adsorption pH of different solutions type its absorption stoste would also vary from.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510769303.4A CN106698577A (en) | 2015-11-12 | 2015-11-12 | Novel method for treating copper ammonia waste etching liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510769303.4A CN106698577A (en) | 2015-11-12 | 2015-11-12 | Novel method for treating copper ammonia waste etching liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106698577A true CN106698577A (en) | 2017-05-24 |
Family
ID=58929556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510769303.4A Withdrawn CN106698577A (en) | 2015-11-12 | 2015-11-12 | Novel method for treating copper ammonia waste etching liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106698577A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502683A (en) * | 2018-12-13 | 2019-03-22 | 江苏国创新材料研究中心有限公司 | A kind of device and copper ion minimizing technology of copper-containing sulfuric acid ammonium salt waste water removal copper ion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052799A (en) * | 1989-04-22 | 1991-07-10 | 时光 | A kind of processing method of strong sorbent |
-
2015
- 2015-11-12 CN CN201510769303.4A patent/CN106698577A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052799A (en) * | 1989-04-22 | 1991-07-10 | 时光 | A kind of processing method of strong sorbent |
Non-Patent Citations (1)
| Title |
|---|
| 张仲燕 等: "含Cu-EDTA废水吸附法处理研究", 《环境科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502683A (en) * | 2018-12-13 | 2019-03-22 | 江苏国创新材料研究中心有限公司 | A kind of device and copper ion minimizing technology of copper-containing sulfuric acid ammonium salt waste water removal copper ion |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hu Lei Inventor before: Xia Dong |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170615 Address after: Jiaxing City, Zhejiang province 314599 Tongxiang City Indus Street Ring Road Fusheng heights 29 Building 2 unit 1201 room Applicant after: Hu Lei Address before: 414400, No. ten, No. 13, Zhenlong village, Miluo, Miluo, Hunan, Yueyang Applicant before: Xia Dong |
|
| TA01 | Transfer of patent application right | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170524 |
|
| WW01 | Invention patent application withdrawn after publication |