CN114604951B - Application of p-tert-octyl phenoxy carboxylic acid in copper-containing wastewater treatment - Google Patents
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- 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
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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Abstract
The invention discloses an application of p-tert-octylphenoxy carboxylic acid in copper-containing wastewater treatment, which has higher selectivity to Cu (II), compared with the existing chemical precipitant, the average particle size of precipitate formed by p-tert-octylphenoxy carboxylic acid and Cu (II) is 109 mu m, and compared with the particle size of precipitate formed by the conventional precipitant and Cu (II), the particle size of the precipitate formed by p-tert-octylphenoxy carboxylic acid and Cu (II) is much larger, and the larger particle size is favorable for separating the precipitate. The p-tert-octyl phenoxy carboxylic acid precipitant has high Cu (II) selectivity, large precipitated particles, high treatment speed, wide temperature adaptability, easy back extraction and recycling, and can dissolve copper by contacting a precipitate formed by the precipitant and copper with low-concentration acid liquid. The copper ion content in the copper-containing wastewater treated by the p-tert-octyl phenoxy carboxylic acid is below 1mg/L, the COD value is less than 105, and the wastewater can reach the discharge standard after the pH value is regulated, so that the wastewater can be used for selectively recycling copper.
Description
Technical Field
The invention belongs to the field of heavy metal ion removal, and particularly relates to application of p-tert-octylphenoxy carboxylic acid in copper-containing wastewater treatment and recovery.
Background
Copper metal is an important industrial resource and is one of the most widely used metals in human society. Copper is widely used in electronic, vehicular, telecommunications, power generation and distribution systems, as well as in household and industrial plumbing, chemicals, money, and general infrastructure due to its good ductility, strength, conductivity, stability, and durability. With the transition of society to lower carbon life, copper will play a more important role in renewable energy infrastructure. However, a large amount of copper-containing heavy metal wastewater is generated during the exploitation of copper ores and the production and use of copper products. Copper is less toxic as a necessary beneficial element for life compared to heavy metals such as Cd, hg, as, pb and Ni. However, copper, like other heavy metals, is not degraded by organisms or chemical actions, and has durability and bioaccumulation. The metal-resistant microorganisms in the water body can enrich metals and be transferred to organisms of all levels through a food chain. Long-term intake of excessive copper in humans can lead to other diseases such as Alzheimer's disease, atherosclerosis, diabetes, etc. Therefore, it is necessary to treat copper-containing heavy metal wastewater before discharging.
Chemical precipitation is the most effective method for treating industrial wastewater and is widely used for removing heavy metals, organic matters, ammonia nitrogen, phosphate, fluorine and sulfide in wastewater. Hydroxide precipitation is the most widely used method for treating heavy metal wastewater. By adding lime, calcium hydroxide, magnesium hydroxide or sodium hydroxide to the wastewater, a metal hydroxide precipitate is formed by increasing the pH of the wastewater. However, the metal hydroxide precipitate formed by the above method is small in particle size, fragile, and requires a long standing time to ensure complete separation of the precipitate. Meanwhile, the treatment period of precipitation is long and heavy metal ions are easy to exceed the emission standard. In order to overcome the technical defects, the prior art mainly adds flocculating agents or seed crystals to accelerate heavy metal precipitation. For example, chareturn tanyarak and the like treat simulated heavy metal wastewater by lime, and after 0.5ppm of polymer is added, not only is hydroxide sedimentation accelerated, but also the removal rate of heavy metal ions is increased. Chen et al obtained larger precipitation particle size by adding fly ash as seed crystal, and remarkably improved sedimentation and heavy metal removal efficiency of sludge. The residual concentrations of chromium, copper, lead and zinc in the wastewater can be reduced to (mg/L) 0.08, 0.14, 0.03 and 0.45, respectively. Sulfide precipitation is a modified method of hydroxide precipitation. Sulfide precipitation has lower solubility and a wider processing pH than hydroxide precipitation. BHATTACHARYA and the like treat the wastewater of an actual copper smelting plant by adopting sodium sulfide, wherein the dosage of the sodium sulfide is 60 percent of the theoretical value, and when the pH value of the effluent is more than 8, the effluent concentration of Cd, cu and Zn is between 0.05 and 0.1mg/l, and the removal rates of As and Se are respectively 98 percent and 92 percent. The separation and recovery of metals by a sulfide precipitation method involves a large number of dynamic chemical reactions and mechanical processes, and the operation process is relatively complex, which is extremely easy to cause the re-dissolution of precipitation and the overflow of toxic hydrogen sulfide gas. In addition, the sulfide precipitate particle size is smaller than that of hydroxide, so that the technical problem of difficult precipitation separation still exists.
Chemical precipitation inevitably produces sludge, which is often sent to professional landfill sites for landfill by enterprises. However, because of the unstable nature of some sludge, heavy metals are released in the landfill process to cause secondary pollution, and thus secondary treatment is often required for the sludge. Currently, the primary treatment methods include curing the sludge with cement and other binders, or rendering the sludge harmless using suitable chemical or biological methods. The above-described methods not only increase the complexity of the process, but also reduce the value of recovering heavy metals from wastewater. Therefore, how to develop a new precipitant capable of being applied to copper-containing wastewater treatment so as to improve the selectivity of the precipitant to copper ions, and the precipitant has the advantages of large precipitation particles, high sedimentation speed, low environmental load, recycling and the like, and the precipitant becomes a technical problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides an application of a p-tert-octylphenoxy carboxylic acid precipitant in copper-containing wastewater treatment.
According to an embodiment of the present invention, the p-tert-octylphenoxy carboxylic acid precipitant is obtained by saponification of alkyl phenoxyacetic acid with hydroxide.
According to an embodiment of the present invention, the alkyl phenoxyacetic acid has a structure as shown in formula (i):
wherein R is 1 Is H or substituted straight-chain alkyl with 1-2 carbon atoms.
According to an embodiment of the present invention, the hydroxide is selected from one or more of magnesium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide.
According to an embodiment of the present invention, the saponification degree of the p-tert-octylphenoxy carboxylic acid precipitant after saponification treatment is 50-100%.
According to an embodiment of the present invention, the saponification treatment may be performed by mechanical grinding or stirring.
The invention also provides a method for treating copper-containing wastewater by using the p-tert-octylphenoxy carboxylic acid precipitant, which comprises the following steps:
a) Mixing the p-tert-octylphenoxy carboxylic acid precipitant with copper-containing wastewater solution, and carrying out solid-liquid separation to obtain a metal precipitate;
b) And eluting the metal precipitate by adopting acid liquor, and separating to obtain a metal enrichment solution and a demetallized precipitate.
According to the invention, the Cu (II) content in the wastewater can be reduced to below 1mg/L through the strong binding capacity of the p-tert-octylphenoxy carboxylic acid precipitant and metal ions, and meanwhile, the COD value of the effluent can be ensured to be less than 105 based on the small water solubility of a complex formed by the Cu (II) and the p-tert-octylphenoxy carboxylic acid precipitant. Thereby realizing that the organic precipitant can remove Cu (II) and COD of effluent water simultaneously reach the standard.
According to the embodiment of the invention, the mole ratio of the p-tert-octylphenoxy carboxylic acid precipitant to copper ions in the copper-containing wastewater is (1.8-2.5): 1, a step of; preferably (2 to 2.2): 1, a step of; exemplary is 1.8: 1. 2: 1. 2.2: 1. 2.5:1.
according to an embodiment of the invention, the copper-containing wastewater has a pH of 2.5 to 5. Preferably 3.
According to the embodiment of the invention, the time for the mixing reaction of the p-tert-octylphenoxy carboxylic acid precipitant and the copper-containing wastewater is 1-30 min; preferably 5 to 10min, and exemplary 1min, 2min, 5min, 8min, 10min, 20min, 30min.
According to the embodiment of the invention, the reaction temperature of the mixed reaction of the p-tert-octylphenoxy carboxylic acid precipitant and the copper-containing wastewater is 25-50 ℃.
According to the embodiment of the invention, the acid liquor is one or more of hydrochloric acid, sulfuric acid and nitric acid, the concentration of the acid liquor is 0.01-12 mol/L, and the molar ratio of the using amount of the acid liquor to the p-tert-octyl phenoxy carboxylic acid precipitant is 1: (0.1-0.5), the eluting temperature of the acid liquor is 25-100 ℃.
According to an embodiment of the present invention, the method for treating copper-containing wastewater with the p-tert-octylphenoxy carboxylic acid precipitant further comprises: the demetallized precipitate reacts with hydroxide to obtain regenerated organic precipitant.
The invention has the beneficial effects that:
(1) The invention provides a novel organic precipitant, namely the treatment effect of tert-octyl phenoxycarboxylic acid on copper-containing heavy metal wastewater, wherein the tert-octyl phenoxycarboxylic acid has higher selectivity on Cu and Cr, zn, ni, mn, mg, and can be preferentially complexed with Cu (II) to form a precipitate. Compared with the existing chemical precipitants, the average particle size of the precipitate formed by the p-tert-octylphenoxy carboxylic acid and Cu (II) is 109 mu m, the particle size of the precipitate formed by the p-tert-octylphenoxy carboxylic acid and Cu (II) is much larger than that of the precipitate formed by the conventional precipitants and Cu (II), and the larger particle size facilitates separation of the precipitate. In the practical operation of wastewater treatment using p-tert-octylphenoxy carboxylic acid, no flocculant is added nor is a sedimentation operation required. This not only reduces the addition of chemicals, but also greatly increases the efficiency of the process.
(2) The p-tert-octylphenoxy carboxylic acid precipitant has a wider temperature application range to Cu (II), and the removal rate of the p-tert-octylphenoxy carboxylic acid to copper ions does not change significantly within the range of 25-50 ℃.
(3) The p-tert-octyl phenoxy carboxylic acid precipitant also has good back extraction capability, and can be contacted with copper and low acid to realize copper dissolution. The p-tert-octyl phenoxyl carboxylic acid can reduce the content of copper ions in copper-containing wastewater to below 1mg/L, ensure that the COD value of the effluent is less than 105, and can reach the discharge standard after the pH is regulated. Therefore, the p-tert-octyl phenoxy carboxylic acid precipitant can be used for selectively recovering copper in heavy metal wastewater mainly containing copper, and has good application prospect.
Drawings
FIG. 1 is a graph showing the particle size distribution of precipitates formed by different precipitants with Cu (II).
FIG. 2 is a graph showing the effect of temperature on the Cu (II) removal performance of the teroctreoxygenate.
FIG. 3 is an infrared spectrum of an initial precipitant and a regenerated precipitant.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The p-tert-octylphenoxyacetic acid used in the following examples of the present invention has a structure shown in the formula (I):
wherein R is 1 For H, the preparation method is referred to as follows:
Enrichment of trace rare earth elements from the leaching liquor of ion-absorption minerals using a solid complex centrifugal separation process.Wang Y.,Guo X.,Bi Y.,Su J.,Kong W.,Sun X.(2018)Green Chemistry,20(9),pp.1998-2006.
the 1mol/L standard NaOH solution was purchased from Shanghai Taitan technologies Inc., and the other reagents used in the experiments were all from the national drug Co. The above reagent grade samples were used without purification. The simulated copper-containing wastewater was prepared by dissolving copper sulfate in deionized water. The pH of the experimental solution was adjusted by 1M NaOH or 2M H 2 SO 4 And (5) solution adjustment.
The concentration of metal ions in the wastewater was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES, iCAP 6500,ULTIMA 2,Horiba Jobin Yvon,French). The acidity of the solution was measured by a digital pH meter pHSJ-4F (INESA Scientific, china, shanghai). The particle size of the metal precipitate was measured on a Mastersizer2000 laser particle size analyzer, uk.
The structure of the initial and regenerated precipitants was characterized by a Nicolet iS50 FT-IR spectrometer (Thermo Fisher, american).
The removal rate (R%) of p-tert-octylphenoxy carboxylic acid to metal ions and the dissolution rate (St%) of metal precipitates were calculated by the formulas (1) and (2):
V feed and V acid Representing the volumes of wastewater and stripping acid, respectively. [ M ]] i And [ M ]] f The initial concentration of the metal ions in the wastewater and the metal concentration of the wastewater after being treated by the precipitant are respectively. S is S t Is the dissolution rate of metal ions in the metal precipitate.
Example 1
10mL of a mixed metal ion solution containing Cu, cr, zn, ni, mn, ca ions and having a pH=3 was taken, the total concentration was 28.32mmol/L, and the concentrations of the metal ions were 4.72mmol/L.
0.1888mmol (50 mg) of p-tert-octylphenoxyacetic acid and 188 mu L of 1mol/L sodium hydroxide were ground and saponified at room temperature, and the saponified p-tert-octylphenoxyacetic acid and the above mixed metal ion solution were mixed at room temperature and stirred sufficiently for 5min, and after precipitation, solid-liquid separation was performed to obtain a mixed metal ion precipitate and an aqueous phase. The results of the removal rate of each metal ion in the mixed metal ion solution of p-tert-octylphenoxyacetic acid after saponification in this example are shown in table 1 below.
TABLE 1 precipitation rate of tert-octylphenoxyacetic acid on common metal ions in wastewater
| Metal ion | Cu | Cr | Zn | Ni | Mn | Ca |
| Removal rate/% | 93.91 | 30.8 | 31.74 | 12.6 | 11.14 | 11.37 |
From the results in table 1, it can be seen that: the removal rate of the saponified p-tert-octylphenoxyacetic acid to copper ions in the mixed metal ion solution is up to 93.91%, and the removal rate of the saponified p-tert-octylphenoxyacetic acid to other metal ions is below 32%. This shows a high selectivity for copper ions and can therefore be used for the selective recovery of copper.
Example 2
0.944mmol (250 mg) of p-tert-octylphenoxyacetic acid was ground and saponified with 944. Mu.L of 1mol/L sodium hydroxide at room temperature, and after saponification, was mixed with 50mL of a 600mg/L aqueous Cu (II) solution at pH=3 and stirred well at room temperature for 5min. The solution with precipitate was directly subjected to particle size distribution testing in a Mastersizer2000 without filtration.
For comparison, under the same experimental conditions, a test was carried out with 0.472mmol of Ca (OH) respectively 2 ，Na 2 S and Na 2 CO 3 Particle size distribution data of the precipitate prepared by mixing with 50ml of 50 mg/L Cu (II) aqueous solution at ph=3 and stirring thoroughly at room temperature for 5min. The results are shown in FIG. 1.
As can be seen from the results in fig. 1: para-tert-octylphenoxyacetic acid, ca (OH) after saponification of this example 2 ，Na 2 S and Na 2 CO 3 The median particle diameters of the precipitate formed with Cu (II) were 109 μm,29 μm,12 μm and 8 μm, respectively. It was thus shown that the particle size of the precipitate formed of p-tert-octylphenoxy carboxylic acid and Cu (II) according to the present invention is much larger than that of the precipitate formed of conventional precipitants and Cu (II), whereas the larger particle size facilitates separation of the precipitate. Therefore, in the practical operation of copper-containing wastewater treatment by using the p-tert-octylphenoxy carboxylic acid, flocculant addition and sedimentation operation are not needed, so that the addition of chemicals can be obviously reduced, and the treatment efficiency can be greatly improved.
In the present invention, the median particle diameter refers to the particle diameter corresponding to a cumulative particle size distribution percentage of one sample reaching 50%. The physical meaning of the particles is that the particles with the particle size larger than the median particle size account for 50 percent, and the particles with the particle size smaller than the median particle size account for 50 percent. The median particle size is often used to represent the average particle size of the powder.
Example 3
0.0944mmol (25 mg) of p-tert-octylphenoxyacetic acid was ground and saponified with 76. Mu.L of 1mol/L sodium hydroxide at room temperature, and after saponification, mixed with 10mL of 300mg/L aqueous Cu (II) solution at pH=3 and stirred thoroughly at different temperatures for 5min. The effect of p-tert-octylphenoxyacetic acid on Cu (II) removal rate when the temperature was increased from 25℃to 50℃at 5℃intervals is shown in FIG. 2.
As can be seen from the results in the graph, the removal rate of the p-tert-octylphenoxyacetic acid on Cu (II) fluctuates in the range of 92.57% and 92.9% at the temperature of 25-50 ℃, and no obvious rising or falling trend exists. Therefore, the p-tert-octyl phenoxy carboxylic acid precipitant has a wider temperature application range for Cu (II).
Example 4
The recovered trioctylphenoxyacetic acid precipitant was obtained by sufficiently contacting trioctylphenoxyacetic acid loaded with 3mg of Cu (II) obtained in example 3 with 10mL of 0.02mol/L sulfuric acid at 25℃for 20min to dissolve out the same with a dissolution rate of 100%.
FIG. 3 is an infrared spectrum of a t-octylphenoxyacetic acid (initial precipitant) and regenerated t-octylphenoxyacetic acid precipitant obtained in this example. From the figure, it can be seen that the regenerated tert-octylphenoxyacetic acid has substantially the same structure as the original tert-octylphenoxyacetic acid, which indicates that the tert-octylphenoxyacetic acid of the present invention has no structural change during Cu (II) removal.
Example 5
0.01076mmol (2.85 mg) of p-tert-octylphenoxyacetic acid were ground and saponified with 10.76mL of 1mol/L sodium hydroxide at room temperature, and after saponification, they were mixed with pH=3, 1L of 300mg/L simulated Cu (II) -containing wastewater and stirred well at room temperature for 5min. Filtering to obtain copper precipitate and treated Cu (II) -containing wastewater. The copper precipitate was dried and then eluted by contact with 10mL of 1mol/L sulfuric acid at 95℃for 20 min. The enriched Cu (II) solution and regenerated precipitant are obtained. The copper content of the treated Cu (II) -containing wastewater residue is 0.81mg/L, and the COD value of the effluent is 65mg/L. The concentration of the obtained enriched Cu (II) solution is 30.21g/L, the dissolution rate of copper precipitate is 97.39 percent, and the enrichment multiple is 100.
Example 6
0.010856mmol (2.875 mg) of p-tert-octylphenoxyacetic acid were ground and saponified with 10.85mL of 1mol/L sodium hydroxide at room temperature, and after saponification, they were mixed with pH=3, 1L of 300mg/L simulated Cu (II) -containing wastewater and stirred well at room temperature for 5min. Filtering to obtain copper precipitate and treated copper-containing wastewater. The copper precipitate was dried and then eluted by contact with 10mL of 1mol/L sulfuric acid at 95℃for 20 min. The enriched copper solution and regenerated precipitant are obtained. The copper content of the treated copper-containing wastewater is 0.31mg/L, and the COD value of the effluent is 102.48mg/L. The concentration of the obtained enriched copper solution is 30.31g/L, the dissolution rate of copper precipitate is 98.99%, and the enrichment multiple is 100.
In conclusion, the invention provides the treatment effect of the novel organic precipitant p-tert-octylphenoxy carboxylic acid on the Cu (II) -containing heavy metal wastewater. Studies show that p-tert-octylphenoxy carboxylic acid has higher selectivity to Cu (II) and can be preferentially complexed with copper to form a precipitate. Compared with the existing chemical precipitant, the average particle size of the precipitate formed by the p-tert-octylphenoxy carboxylic acid and copper is 109 mu m, which is far larger than that of the conventional chemical precipitant. Thus, the precipitate can be separated without the addition of a flocculant or sedimentation. The treatment rate is more efficient than existing chemical precipitants. The p-tert-octylphenoxy carboxylic acid precipitant has a wide temperature application range, the temperature is changed within 25-50 ℃, the Cu (II) removal rate of the p-tert-octylphenoxy carboxylic acid is not changed obviously, and the p-tert-octylphenoxy carboxylic acid precipitant also has good dissolution capacity, can realize the dissolution of most of copper by contact with low acid, and realizes the circulation of the precipitant. The copper ion content in the copper-containing wastewater treated by the p-tert-octyl phenoxy carboxylic acid is below 1mg/L, the COD value is less than 105, and the wastewater can reach the discharge standard after the pH is regulated. Therefore, the tert-octyl phenoxy carboxylic acid precipitant can be used for selectively recovering copper in heavy metal wastewater mainly containing copper, and has good application prospect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The use of a p-tert-octylphenoxy carboxylic acid precipitant in the treatment of copper-containing wastewater,
the p-tert-octylphenoxy carboxylic acid precipitant is obtained by saponification of alkyl phenoxyacetic acid with hydroxide, and the saponification degree of the p-tert-octylphenoxy carboxylic acid precipitant after saponification is 50-100%;
the alkyl phenoxyacetic acid has a structure shown in a formula (I):
wherein R is 1 Is H or substituted C1-2A linear alkyl group.
2. The use according to claim 1, wherein the hydroxide is selected from one or more of magnesium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide.
3. The use according to claim 1 or 2, wherein the saponification treatment is performed by mechanical grinding or stirring.
4. A method for treating copper-containing wastewater with p-tert-octylphenoxy carboxylic acid precipitants for use according to any one of claims 1 to 3, comprising the steps of:
a) Mixing the p-tert-octylphenoxy carboxylic acid precipitant with copper-containing wastewater solution, and carrying out solid-liquid separation to obtain a metal precipitate;
b) And eluting the metal precipitate by adopting acid liquor, and separating to obtain a metal enrichment solution and a demetallized precipitate.
5. The method for treating copper-containing wastewater as claimed in claim 4, wherein a molar ratio of the p-tert-octylphenoxy carboxylic acid precipitant to copper ions in the copper-containing wastewater is (1.8 to 2.5): 1.
6. the method for treating copper-containing wastewater according to claim 5, wherein the molar ratio of p-tert-octylphenoxy carboxylic acid precipitant to copper ions in the copper-containing wastewater is (2 to 2.2): 1.
7. the method for treating copper-containing wastewater according to any one of claims 5 to 6, wherein the pH of the copper-containing wastewater is 2.5 to 5.
8. The method for treating copper-containing wastewater according to any one of claims 5 to 6, wherein the p-tert-octylphenoxy carboxylic acid precipitant is mixed with the copper-containing wastewater for a reaction time of 1 to 30 minutes.
9. The method for treating copper-containing wastewater as claimed in claim 8, wherein the p-tert-octylphenoxy carboxylic acid precipitant is mixed with the copper-containing wastewater for a reaction time of 5 to 10 minutes.
10. The method for treating copper-containing wastewater as claimed in any one of claims 5 to 6, wherein the reaction temperature of the mixed reaction of the p-tert-octylphenoxy carboxylic acid precipitant and the copper-containing wastewater is 25 to 50 ℃.
11. The method according to any one of claims 5 to 6, wherein the acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid, the concentration of the acid solution is 0.01 to 12mol/L, and the elution temperature of the acid solution for elution is 25 to 100 ℃.
12. The method of treating copper-containing wastewater of any of claims 5-6, wherein the method of treating copper-containing wastewater further comprises: the demetallized precipitate reacts with hydroxide to obtain regenerated organic precipitant.
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| CN111041203A (en) * | 2019-12-27 | 2020-04-21 | 厦门钨业股份有限公司 | Mixed extracting agent for nickel-lithium separation and separation method |
| CN111747985A (en) * | 2020-06-08 | 2020-10-09 | 厦门稀土材料研究所 | Preparation and application of phenoxy dicarboxylic acid type functionalized ionic liquid |
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