CN111499029A - Two-stage method for quickly removing copper ions in copper ammonia complex wastewater - Google Patents
Two-stage method for quickly removing copper ions in copper ammonia complex wastewater Download PDFInfo
- Publication number
- CN111499029A CN111499029A CN202010166365.7A CN202010166365A CN111499029A CN 111499029 A CN111499029 A CN 111499029A CN 202010166365 A CN202010166365 A CN 202010166365A CN 111499029 A CN111499029 A CN 111499029A
- Authority
- CN
- China
- Prior art keywords
- copper
- wastewater
- ammonia
- stage
- complex
- 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
Images
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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
⑴ adding alkali into the waste water to adjust the waste water to proper pH value, to break the first section of complex deposit to remove part of copper, with the chemical reaction formula as follows:
⑵ adding hydroxamic acid type separating agent into the copper-containing suspension, mixing, standing, two-stage deep chelating to remove copper and flocculating settling to separate, and chelating reaction formula [ Cu (NH)3)4]2++RCONHO‑→RCONHOCu↓+NH3·H2OCu(OH)2+RCONHO‑→RCONHO‑Cu(OH)2And ↓and ⑶ sediment underflow is high content copper mud, after taking out, high purity copper hydroxide powder is formed by dehydration and drying, filtrate and supernatant overflow to enter the subsequent deamination system.
Description
Technical Field
The invention belongs to the field of sewage treatment, relates to a method for quickly removing copper ions in copper ammonia complex wastewater, and particularly relates to a method for quickly removing copper ions in copper ammonia cleaning wastewater produced in an alkaline etching process of a printed circuit board and recovering copper resources.
Background
Alkaline etching is a commonly adopted process in the production of Printed Circuit Boards (PCBs), a large amount of alkaline washing water containing copper-ammonia complex and free ammonia is generated in the subsequent cleaning process, and accounts for about 3-5% of the total amount of wastewater generated by the PCBs, the wastewater is dark blue, the pH value is about 8.5-9.5, the copper ion content is 100-1000 mg/L, the ammonia nitrogen content is 500-5000 mg/L, and the alkaline washing water has great harm to water environment and human bodies and needs to be effectively treated.
The free copper-containing wastewater is easier to remove by a common chemical precipitation method, but the copper ammonia wastewater mainly containing low-concentration complex copper and medium-concentration ammonia nitrogen is difficult to treat by a conventional method, and is generally removed by adding agents such as sodium sulfide, ferrous sulfate, PAC (polyaluminium chloride), PAM (polyacrylamide) and the like after being mixed and diluted with a large amount of other types of wastewater for precipitation. In order to reduce the copper ion residue in the wastewater and improve the flocculation sedimentation performance of the precipitated particle slurry, excessive sodium sulfide and ferrous sulfate are added, and a large amount of medicament is consumed in repeatedly adjusting the pH value of the wastewater, so that a large amount of dangerous waste sludge with more impurities and lower copper content (about 3-5%) is generated, and the dangerous waste sludge still needs to be handed over to an enterprise with related qualification for special treatment, thereby increasing the wastewater treatment cost, and causing the waste of copper resources and potential risks of subsequent treatment. Meanwhile, the whole ammonia nitrogen content of the wastewater after dilution and mixing treatment is still high, and the wastewater is difficult to be effectively treated by the existing biochemical facilities, so that great burden and pressure are caused to final water drainage of a plant area.
Therefore, the property characteristics of the copper ammonia complex wastewater are fully utilized, based on the copper ammonia complex reaction-chemical equilibrium theory, the copper ion pollution is removed in a proper mode, the copper ion pollution is recovered in a copper-containing byproduct form, favorable conditions are created for subsequent ammonia nitrogen treatment, and the method is very necessary and valuable. Meanwhile, because the hydroxamic acid functional group (R-CONHOH) has stronger chelating adsorption capacity on transition metals (such as copper and iron elements) and rare earth elements, the hydroxamic acid type reagent is commonly used as a collector for rare earth mineral flotation and a flocculating agent for red mud sedimentation in alumina production, but the hydroxamic acid type separating reagent is not reported to be used for copper ammonia wastewater treatment.
Disclosure of Invention
The invention aims to solve the problems that the removal of complex copper in the cleaning wastewater after the existing PCB alkaline etching is difficult, the treatment cost is high, the copper resource cannot be effectively recycled and the like, and provides a two-stage method for quickly removing the copper ions in the copper ammonia complex wastewater, which can realize the decomplexation of the copper ammonia complex ions in the wastewater and the quick precipitation removal of the copper ions by controlling the pH value of the wastewater and adding a hydroxamic acid type separating agent and can recover the copper resource in the wastewater in the form of high-purity copper hydroxide.
The technical scheme of the invention is that the two-stage method for rapidly removing the copper ions in the copper ammonia complexing wastewater is characterized by comprising a first-stage alkaline decomplexation precipitation and a second-stage deep chelation-flocculation; the method comprises the following steps:
⑴ according to the concentration of copper and ammonia nitrogen in the wastewater, the copper ammonia complex ions are decomplexed by using the difference of chemical reaction equilibrium constants through one-stage alkali adjustment, and the degree of reaction crystallization is controlled to form copper hydroxide fine particles;
⑵ Oxime acid type separating agent is added and quickly separated and removed by a two-stage deep chelating-flocculating method.
Preferably, the alkali used in the alkali adjustment in the step ⑴ is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide, preferably sodium hydroxide, and the pH of the cuprammonium wastewater is adjusted to be greater than 10, preferably to be between 11 and 13.
Preferably, the step ⑴ further comprises the steps of adding 200 g/L of alkali into the cuprammonia complexing wastewater, adjusting the pH value of the wastewater to 11.80-12.10, and performing primary complexation breaking precipitation to remove part of copper, wherein the chemical reaction formula is as follows:
preferably, the step ⑴ further comprises the step of removing copper from the industrial cuprammonium wastewater by using a continuous precipitation tank, wherein a sodium hydroxide solution with the mass concentration of 35% is gradually added into the reaction tank under mechanical stirring, the pH value of the wastewater is controlled to be 11.80-11.95, and the retention time is 60 min.
Preferably, in step ⑵, the hydroxamic acid type separating agent component is an organic high molecular polymer containing hydroxamic acid functional groups, the content of the hydroxamic acid functional groups is 5-30%, the molecular weight is more than 100 ten thousand, and the dosage is 0.1-0.001%, preferably 0.02-0.002% of the total amount of the wastewater.
Preferably, the step ⑵ further comprises gradually adding 30 mg/L of hydroxamic acid type separating agent solution into the coagulation tank, wherein the retention time is 20min, then the wastewater enters the sedimentation separation tank and stays for 60min to 100min, the residual solid content in the overflow of the sedimentation separation tank is 2.4 mg/L to 5.8 mg/L, the copper content in the filtered water sample is 3.6 mg/L to 6.9 mg/L, and the copper removal rate is 99.1 to 99.3 percent.
Preferably, the step ⑵ further comprises adding hydroxamic acid type separating agent into the obtained copper-containing suspension, mixing uniformly, standing, and performing two-stage deep chelating copper removal and flocculation settling separation;
the chelation reaction formula is as follows:
[Cu(NH3)4]2++RCONHO-→RCONHOCu↓+NH3·H2O
Cu(OH)2+RCONHO-→RCONHO-Cu(OH)2↓。
preferably, the method also comprises a step ⑶ of settling underflow, namely copper-containing mud, wherein the solid content of the underflow is higher than 5% before dehydration, the underflow is taken out and dehydrated and dried to form copper hydroxide powder with the purity of 95% and the copper content of 63%, the copper hydroxide powder is used as a raw material of related copper-containing reagents, preferably used as an agricultural copper hydroxide bactericide, and filtrate and supernatant overflow to a subsequent deamination system.
Preferably, the method comprises the following steps: the treated copper ammonia wastewater is cleaning wastewater after printed circuit alkaline etching, and comprises copper ammonia complex and free ammonia; the treated overflow and filtrate are ammonia nitrogen wastewater after copper removal, and directly enter ammonia nitrogen treatment systems such as stripping and membrane separation, or enter a biochemical treatment system after dilution, preferably directly enter the ammonia nitrogen membrane separation system.
Preferably, the solid content of the copper-containing slurry obtained after copper deposition treatment of the cuprammonium wastewater is 80 g/L-210 g/L, after filtration, washing and drying, the average particle size is 1.85-2.32 μm through laser particle size analysis, the copper-containing slurry is crystalline copper hydroxide through X-ray diffraction analysis, and the content of the copper-containing slurry is 98.3-99.1% in terms of copper hydroxide through fluorescence spectrum analysis.
The other technical scheme of the invention is that the two-stage method for quickly removing the copper ions in the copper ammonia complexing wastewater is characterized by comprising the following steps:
(1) adding 10-40% alkali into the cuprammonia complexing wastewater to adjust the wastewater to a proper pH value, carrying out first-stage complex breaking precipitation to remove part of copper, wherein the chemical reaction formula is as follows:
(2) adding hydroxamic acid type separating agent accounting for 0.1-0.001% of the total amount of the wastewater into the obtained copper-containing suspension, uniformly mixing, standing, and performing two-stage deep chelation copper removal and flocculation sedimentation separation;
the chelation reaction formula is as follows:
[Cu(NH3)4]2++RCONHO-→RCONHOCu↓+NH3·H2O
Cu(OH)2+RCONHO-→RCONHO-Cu(OH)2↓
the flocculation mechanism is as follows:
(3) taking out the settled bottom flow which is the copper-containing slurry, and dehydrating and drying the bottom flow to form copper hydroxide powder; and overflowing the filtrate and the supernatant into a subsequent deamination system.
Compared with the prior art, the invention has the beneficial effects that:
⑴ the method is simple, high in copper removal rate and low in comprehensive cost, and can promote the subsequent ammonia nitrogen treatment.
⑵ the invention only adds alkali and hydroxamic acid separating agent on the basis that the waste water is alkaline, which can avoid the problems of easy agent residue, poor water quality, poor precipitation effect and excessive sludge caused by adding ferrous sulfate, sodium sulfide, conventional flocculant and repeated pH adjustment in the conventional treatment method.
⑶ the by-product of the invention is copper hydroxide particles with high purity, good dispersibility and high added value.
⑷ the invention is beneficial to the follow-up treatment of ammonia nitrogen pollutants and can be used as a key basic link for the cooperative treatment of cuprammonia waste water.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic illustration of the flocculation mechanism of the present invention;
FIG. 3 is a schematic representation of the results of XRD of a by-product of the present invention;
FIG. 4 is a photograph of a sample of the by-product copper hydroxide recovered by the present invention.
Detailed Description
The invention will be further described in detail with reference to the following examples:
the two-stage method for quickly removing the copper ions in the copper ammonia complexing wastewater is characterized by comprising the following steps of:
⑴ adding alkali into the cuprammonia complexing wastewater to adjust the wastewater to a proper pH value, and performing a first-stage complex breaking precipitation to remove part of copper, wherein the chemical reaction formula is as follows:
⑵ adding hydroxamic acid type separating agent into the copper-containing suspension, mixing, standing, and performing two-stage deep chelating copper removal and flocculation settling separation.
The chelation reaction formula is as follows:
[Cu(NH3)4]2++RCONHO-→RCONHOCu↓+NH3·H2O
Cu(OH)2+RCONHO-→RCONHO-Cu(OH)2↓
the flocculation mechanism is shown in figure 2;
(3) and taking out the settled underflow, namely the copper-containing slurry, and dehydrating and drying the underflow to form copper hydroxide powder. And overflowing the filtrate and the supernatant into a subsequent deamination system.
The cuprammonium wastewater used in examples 1-3 was a self-made cuprammonium solution, and the components are shown in table 1; the cuprammonium waste water used in examples 4-6 is cuprammonium cleaning waste water generated in the alkaline etching process in the actual production of Shenzhen electronic factory, and the composition is shown in Table 2.
TABLE 1 self-made cuprammonium solution composition
| Composition (I) | Cu2+ | NH4-N | Cl- | pH |
| Content mg/L | 201.4 | 1422.0 | 240.0 | 8.90 |
TABLE 2 composition of waste water containing copper and ammonia from alkaline etching line of PCB manufacturer
| Composition (I) | Cu2+ | NH4-N | Cl- | pH |
| Content mg/L | 507.5 | 1980.0 | 3100.0 | 9.15 |
Example 1
Referring to fig. 1, sodium hydroxide solution (200 g/L) is added dropwise into the self-made cuprammonia wastewater, the pH value of the wastewater is adjusted to 11.80, 50 mg/L hydroxamic acid type separating agent solution is added after stirring reaction for 30min, standing and settling are carried out for 15min, the residual solid content of supernatant is 3.5 mg/L, the copper content in a filtered water sample is 1.6 mg/L, and the copper removal rate is 99.2%.
Example 2
Referring to fig. 1, sodium hydroxide solution (200 g/L) is added dropwise into the self-made cuprammonia wastewater, the pH value of the wastewater is adjusted to 12.10, 80 mg/L hydroxamic acid type separating agent solution is added after stirring reaction for 30min, standing and settling are carried out for 15min, the residual solid content of supernatant is 2.7 mg/L, the copper content in a filtered water sample is 1.1 mg/L, and the copper removal rate is 99.4%.
Example 3
Referring to fig. 1, after copper precipitation treatment is performed on the self-made cuprammonium wastewater, the solid content of the obtained copper-containing slurry is about 80 g/L, and after filtration, washing and drying, the average particle size is 2.32 μm by laser particle size analysis, the copper-containing slurry is crystalline copper hydroxide (as shown in fig. 4) by X-ray diffraction analysis, and the content of the copper hydroxide is 99.1% by fluorescence spectrum analysis.
Example 4
Referring to fig. 1, a continuous precipitation tank is adopted to remove copper from industrial cuprammonium wastewater, sodium hydroxide solution with the mass concentration of 35% is gradually added into a reaction tank under mechanical stirring, the pH value of the wastewater is controlled to be 11.80, the retention time is about 60min, hydroxamic acid type separating agent solution is gradually added into a coagulation tank, the dosage is about 30 mg/L, the retention time is 20min, then the wastewater enters a settling separation tank to stay for about 60min, the residual solid content in overflow of the settling separation tank is 5.8 mg/L, the copper content in a filtered water sample is 6.9 mg/L, and the copper removal rate is 99.1%.
Example 5
Referring to fig. 1, a continuous precipitation tank is adopted to remove copper from industrial cuprammonium wastewater, sodium hydroxide solution with the mass concentration of 35% is gradually added into a reaction tank under mechanical stirring, the pH value of the wastewater is controlled to be 11.95, the retention time is about 60min, hydroxamic acid type separating agent solution is gradually added into a coagulation tank, the dosage is about 30 mg/L, the retention time is 20min, then the wastewater enters a settling separation tank to stay for about 100min, the residual solid content in overflow of the settling separation tank is 2.4 mg/L, the copper content in a filtered water sample is 3.6 mg/L, and the copper removal rate is 99.3%.
Example 6
Referring to fig. 1, the solid content of the copper-containing slurry obtained by the copper deposition treatment of the industrial cuprammonium wastewater is about 210 g/L, and the sample obtained by filtering, washing and drying is shown in fig. 4, wherein the average particle size is 1.85 μm by laser particle size analysis, the sample is crystalline copper hydroxide by X-ray diffraction analysis, and the content of the copper hydroxide is 98.3% by fluorescence spectrum analysis.
The above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (11)
1. A two-stage method for quickly removing copper ions in copper ammonia complexing wastewater is characterized by comprising a first-stage alkaline decomplexation precipitation and a second-stage deep chelation-flocculation; the method comprises the following steps:
⑴ according to the concentration of copper and ammonia nitrogen in the wastewater, the copper ammonia complex ions are decomplexed by using the difference of chemical reaction equilibrium constants through one-stage alkali adjustment, and the degree of reaction crystallization is controlled to form copper hydroxide fine particles;
⑵ Oxime acid type separating agent is added and quickly separated and removed by a two-stage deep chelating-flocculating method.
2. The two-stage method for rapidly removing the copper ions from the copper ammonia complexing wastewater according to claim 1, wherein the alkali used in the alkali adjustment in the step ⑴ is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide, preferably sodium hydroxide, and the pH of the copper ammonia wastewater is adjusted to be greater than 10, preferably to be 11-13.
3. The two-stage method for rapidly removing the copper ions in the cuprammonia complexing wastewater according to claim 2, wherein the step ⑴ further comprises the steps of adding 200 g/L of alkali into the cuprammonia complexing wastewater, adjusting the pH value of the wastewater to 11.80-12.10, and performing one-stage complex breaking precipitation to remove part of copper, wherein the chemical reaction formula is as follows:
4. the two-stage method for rapidly removing the copper ions in the copper ammonia complex wastewater according to claim 1, wherein the step ⑴ further comprises the step of removing the copper from the industrial copper ammonia wastewater by using a continuous precipitation tank, wherein a sodium hydroxide solution with the mass concentration of 35% is gradually added into a reaction tank under mechanical stirring, the pH value of the wastewater is controlled to be 11.80-11.95, and the retention time is 60 min.
5. The method for rapidly removing the copper ions from the copper ammonia complex wastewater by the two-stage process according to claim 1, wherein the hydroxamic acid type separating agent in the step ⑵ is an organic high molecular polymer containing hydroxamic acid groups, the content of the hydroxamic acid groups is 5-30%, the molecular weight is more than 100 ten thousand, and the consumption is 0.1-0.001%, preferably 0.02-0.002% of the total amount of the wastewater.
6. The two-stage method for rapidly removing the copper ions in the copper ammonia complex wastewater as claimed in claim 1, wherein the step ⑵ further comprises the steps of gradually adding 30 mg/L hydroxamic acid type separating agent solution into a coagulation tank, allowing the solution to stay for 20min, allowing the wastewater to enter a settling separation tank, allowing the wastewater to stay for 60min to 100min, allowing the residual solid content in overflow of the settling separation tank to be 2.4 mg/L to 5.8 mg/L, allowing the copper content in a filtered water sample to be 3.6 mg/L to 6.9 mg/L, and allowing the copper removal rate to be 99.1% to 99.3%.
7. The two-stage method for rapidly removing the copper ions in the copper ammonia complex wastewater according to claim 5 or 6, wherein the step ⑵ further comprises the steps of adding a hydroxamic acid type separating agent into the obtained copper-containing suspension, uniformly mixing, standing, and performing two-stage deep chelating copper removal and flocculation settling separation;
the chelation reaction formula is as follows:
[Cu(NH3)4]2++RCONHO-→RCONHOCu↓+NH3·H2O
Cu(OH)2+RCONHO-→RCONHO-Cu(OH)2↓。
8. the two-stage process for removing copper ions from the waste water containing copper and ammonia complex according to claim 1, further comprising ⑶, the settled bottom flow is copper-containing slurry, the solid content of the bottom flow is higher than 5% before dehydration, the bottom flow is dehydrated and dried after being taken out to form copper hydroxide powder with purity of 95% and copper content of 63%, the copper hydroxide powder is used as raw material of related copper-containing reagent, preferably used as agricultural copper hydroxide bactericide, and the filtrate and supernatant overflow to a subsequent deamination system.
9. The two-stage method for rapidly removing the copper ions in the copper ammonia complex wastewater according to claim 8, wherein the treated copper ammonia wastewater is the cleaning wastewater after the alkaline etching of the printed circuit and comprises the components of a copper ammonia complex and free ammonia; the treated overflow and filtrate are ammonia nitrogen wastewater after copper removal, and directly enter ammonia nitrogen treatment systems such as stripping and membrane separation, or enter a biochemical treatment system after dilution, preferably directly enter the ammonia nitrogen membrane separation system.
10. The method for rapidly removing the copper ions in the cuprammonium complex wastewater according to claim 8, wherein the copper-containing slurry obtained by the cuprammonium complex wastewater after the cuprammonium complex wastewater is subjected to copper precipitation treatment contains 80 g/L-210 g/L of solid, and after the copper-containing slurry is filtered, washed and dried, the average particle size is 1.85 μm-2.32 μm as shown by laser particle size analysis, the copper-containing slurry is crystalline copper hydroxide as shown by X-ray diffraction analysis, and the content of the copper-containing slurry is 98.3% -99.1% as shown by fluorescence spectrum analysis.
11. A two-stage method for quickly removing copper ions in copper ammonia complexing wastewater is characterized by comprising the following steps:
⑴ adding 10-40 wt% alkali into the cuprammonia complexing wastewater to adjust the wastewater to a proper pH value, and performing first-stage complex breaking precipitation to remove part of copper, wherein the chemical reaction formula is as follows:
⑵ adding hydroxamic acid type separating agent with the total amount of wastewater of 0.1-0.001% into the obtained copper-containing suspension, mixing uniformly, standing, and performing two-stage deep chelating copper removal and flocculation settling separation;
the chelation reaction formula is as follows:
[Cu(NH3)4]2++RCONHO-→RCONHOCu↓+NH3·H2O
Cu(OH)2+RCONHO-→RCONHO-Cu(OH)2↓
the flocculation mechanism is as follows:
⑶ and dewatering and drying to obtain copper hydroxide powder, and overflow of filtrate and supernatant to the subsequent deaminizing system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010166365.7A CN111499029B (en) | 2020-03-11 | 2020-03-11 | Two-stage method for quickly removing copper ions in copper ammonia complexing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010166365.7A CN111499029B (en) | 2020-03-11 | 2020-03-11 | Two-stage method for quickly removing copper ions in copper ammonia complexing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111499029A true CN111499029A (en) | 2020-08-07 |
| CN111499029B CN111499029B (en) | 2022-05-13 |
Family
ID=71865457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010166365.7A Active CN111499029B (en) | 2020-03-11 | 2020-03-11 | Two-stage method for quickly removing copper ions in copper ammonia complexing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111499029B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299594A (en) * | 2020-10-09 | 2021-02-02 | 常州大学 | Integrated device and method for pretreating copper ammonia wastewater |
| CN112980049A (en) * | 2021-03-24 | 2021-06-18 | 重庆先为纤行智能科技有限公司 | Hybrid modification method for in-situ copper removal of non-metal powder of printed circuit board and composite material |
| CN114790049A (en) * | 2022-02-25 | 2022-07-26 | 深圳市臻鼎环保科技有限公司 | Copper removal treatment process for copper ammonia wastewater |
| CN114804193A (en) * | 2022-04-13 | 2022-07-29 | 攀枝花学院 | Method for removing iron from low-concentration industrial titanium liquid and method for preparing high-purity titanium dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102466637A (en) * | 2010-11-01 | 2012-05-23 | 袁俊海 | Method for measuring static ion removal rate of hydroxamic acid type polymeric chelant |
| CN102765829A (en) * | 2011-05-04 | 2012-11-07 | 上海焦化有限公司 | Treatment method for urea-containing high concentration copper ammonium wastewater |
| CN103466770A (en) * | 2013-09-27 | 2013-12-25 | 中南大学 | Copper ammonia complexation wastewater treatment method |
-
2020
- 2020-03-11 CN CN202010166365.7A patent/CN111499029B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102466637A (en) * | 2010-11-01 | 2012-05-23 | 袁俊海 | Method for measuring static ion removal rate of hydroxamic acid type polymeric chelant |
| CN102765829A (en) * | 2011-05-04 | 2012-11-07 | 上海焦化有限公司 | Treatment method for urea-containing high concentration copper ammonium wastewater |
| CN103466770A (en) * | 2013-09-27 | 2013-12-25 | 中南大学 | Copper ammonia complexation wastewater treatment method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299594A (en) * | 2020-10-09 | 2021-02-02 | 常州大学 | Integrated device and method for pretreating copper ammonia wastewater |
| CN112299594B (en) * | 2020-10-09 | 2022-05-13 | 常州大学 | Integrated device and method for pretreating copper ammonia wastewater |
| CN112980049A (en) * | 2021-03-24 | 2021-06-18 | 重庆先为纤行智能科技有限公司 | Hybrid modification method for in-situ copper removal of non-metal powder of printed circuit board and composite material |
| CN114790049A (en) * | 2022-02-25 | 2022-07-26 | 深圳市臻鼎环保科技有限公司 | Copper removal treatment process for copper ammonia wastewater |
| CN114804193A (en) * | 2022-04-13 | 2022-07-29 | 攀枝花学院 | Method for removing iron from low-concentration industrial titanium liquid and method for preparing high-purity titanium dioxide |
| CN114804193B (en) * | 2022-04-13 | 2023-09-22 | 攀枝花学院 | Method for removing iron from low-concentration industrial titanium liquid and method for preparing high-purity titanium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111499029B (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111499029B (en) | Two-stage method for quickly removing copper ions in copper ammonia complexing wastewater | |
| US10633272B2 (en) | Recovery of phosphorus compounds from wastewater | |
| US20130168314A1 (en) | Method for Treating Wastewater Containing Copper Complex | |
| CN102259996B (en) | Method for treating copper-containing waste water | |
| CN105000713A (en) | Desulfurization wastewater treatment system and desulfurization wastewater treatment method | |
| CN105540988A (en) | Effluent treatment technology and system based on combination of super magnetic separation and microwave energy technology | |
| CN111573806A (en) | Deep fluorine removal agent and preparation method and application thereof | |
| CN110683676A (en) | Copper-containing printed circuit board wastewater treatment method | |
| CN111217484A (en) | Desulfurization wastewater recycling treatment method | |
| CN110759532A (en) | High-salt concentrated water treatment process for producing iron phosphate by sodium method | |
| CN112960811A (en) | Resourceful pretreatment system and method for desulfurization wastewater of coal-fired power plant | |
| JP5118572B2 (en) | Sewage treatment method | |
| CA2647965C (en) | Nickel sulphide precipitation processes | |
| CN111675295A (en) | Preparation method of efficient flocculant for purifying acid mine wastewater | |
| CN111439767A (en) | Efficient preparation method for preparing aluminum sulfate by using waste | |
| JP3945216B2 (en) | Waste acid gypsum manufacturing method | |
| CN110862172A (en) | Comprehensive purification system and method for desulfurization wastewater by limestone-gypsum method | |
| CN103007588B (en) | The method of the ammonium sulfate liquor purification that a kind of sintering flue gas ammonia method desulfurizing technique produces | |
| CN215049255U (en) | Resourceful pretreatment system of coal fired power plant desulfurization waste water | |
| CN212403800U (en) | Coal fired power plant desulfurization waste water integrated processing system | |
| CN112158896A (en) | Efficient wet desulphurization wastewater treatment water purifying agent and application thereof | |
| CN112062366A (en) | Coal-fired power plant desulfurization wastewater comprehensive treatment system and method | |
| CN113072230A (en) | Heavy metal wastewater treatment method for aluminum product production | |
| CN111333219A (en) | Online purification and recycling method of PCB washing wastewater | |
| CN111362460A (en) | Efficient recycling treatment method for reclaimed water of thermal power plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |