CN110759521B - Method for treating low-concentration copper-containing wastewater - Google Patents
Method for treating low-concentration copper-containing wastewater Download PDFInfo
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- CN110759521B CN110759521B CN201910982400.XA CN201910982400A CN110759521B CN 110759521 B CN110759521 B CN 110759521B CN 201910982400 A CN201910982400 A CN 201910982400A CN 110759521 B CN110759521 B CN 110759521B
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- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011812 mixed powder Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000003403 water pollutant Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
- 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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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
- 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)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating low-concentration copper-containing wastewater, which comprises the following steps: 1) uniformly mixing metal aluminum powder and silicon dioxide particles, and then grinding to obtain mixed powder; 2) adjusting the pH value of the copper-containing wastewater to 5-9, adding the mixed powder obtained in the step 1), stirring for reaction, and carrying out solid-liquid separation to obtain copper-containing slag and a copper-removed liquid. The treatment method provided by the invention can realize deep removal of copper ions in the wastewater, completely meets the concentration requirement of direct discharge of water pollutants in GB25467-2010 on total copper, and has the advantages of short copper removal process flow, simple operation and easy industrial application.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to a treatment method of low-concentration copper-containing wastewater.
Background
The copper-containing wastewater has wide sources, a large amount of copper-containing wastewater is produced in the mining, ore dressing, smelting, electroplating industries and the like of nonferrous metals, the change range of the copper concentration is large, and the copper content in each liter of wastewater is from dozens of milligrams to several grams. The discharge of the copper-containing wastewater not only causes the waste of copper resources, but also causes persistent pollution to the ecological environment, and seriously threatens the natural environment and human health.
The traditional treatment method mainly comprises a lime neutralization method, a sulfide precipitation method, an extraction method, a biological method and the like, and the methods have the problems of low treatment efficiency, high secondary pollution, high energy consumption, complex operation procedures and the like, for example, the lime neutralization method commonly applied in China at present has an industrial application rate of over 90 percent, but the calcium sulfate, heavy metal oxide and other sediments generated after treatment by the method are large in amount and difficult to dehydrate, have large occupied area, and are easy to cause secondary dissolution of the heavy metal oxide through simple stockpiling treatment, so that the secondary pollution of the water body is caused. Although the sulfurization precipitation method has the advantage of large pH value adaptation range, the sulfurization agent is expensive, and toxic hydrogen sulfide gas is generated in the precipitation process, so that certain potential safety hazards exist. With the strictness of the national environmental protection policy, a simple and efficient copper-containing wastewater treatment process is urgently needed.
Disclosure of Invention
In view of the above, the present invention provides a method for treating low-concentration copper-containing wastewater. The method provided by the invention can treat the copper-containing wastewater through a short process flow, so that the Cu in the treated liquid can be treated2+The concentration is lower than 0.5ppm, and the concentration requirement of direct discharge of water pollutants on total copper in the national standard GB25467-2010 is completely met.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for treating low-concentration copper-containing wastewater comprises the following steps:
1) uniformly mixing metal aluminum powder and silicon dioxide particles, and then grinding to obtain mixed powder;
2) adjusting the pH value of the copper-containing wastewater to 5-9, adding the mixed powder obtained in the step 1), stirring for reaction, and carrying out solid-liquid separation to obtain copper-containing slag and a copper-removed liquid.
Preferably, in the step 1), the mass ratio of the metal aluminum powder to the silicon dioxide particles is 1: 1-9: 1.
Preferably, in the step 1), the grinding is specifically carried out in a vibration ball mill for 1-15 min.
Preferably, Cu in the copper-containing wastewater2+The concentration of (b) is 0.1-2 g/L.
Preferably, in the step 2), the mass-to-volume ratio of the mixed powder to the copper-containing wastewater is 0.1-1 g: 100 ml.
Preferably, in the step 2), the temperature of the stirring reaction is 25-50 ℃, and the time of the stirring reaction is 0.5-2 hours.
Preferably, in the step 2), Cu in the copper-removed solution2+Is less than 0.5 ppm.
The invention has the beneficial effects that:
(1) grinding to obtain Al/SiO2Mixing the powders and then based on Al/SiO2High reactivity of the mixed powder to Cu in copper-containing wastewater2+Act so that Cu2+The copper ions in the treated wastewater are less than 0.5ppm, so that the copper ions in the wastewater are deeply removed, and the requirement of direct discharge of water pollutants in GB25467-2010 on the concentration of total copper is completely met;
(2) the copper removal process is short in flow, simple to operate and easy for industrial application.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
The low-concentration copper-containing wastewater comes from a smelting plant, wherein the pH value of the wastewater is 9 and Cu is measured2+The concentration was 0.1 g/L. Firstly, 10g of metal aluminum powder and 10g of silicon dioxide particles are put into a vibration ball mill for mixing and ball milling, and after ball milling is carried out for 10min, the obtained mixed powder is cooled to room temperature for later use; adding 0.1g of mixed powder into 100ml of low-concentration copper-containing wastewater, stirring at 30 ℃ for reaction for 1.5h, filtering to obtain copper-containing slag and a solution after copper removal, and detecting and analyzing by a plasma spectrometer to obtain Cu in the solution after copper removal2+The concentration was 0.32 ppm.
Example 2
The low concentration copper-containing wastewater is from an electroplating plant, wherein the pH of the wastewater is measured to be 3, and Cu is measured2+The concentration was 0.58 g/L. Firstly, 18g of metal aluminum powder and 2g of silicon dioxide particles are put into a vibration ball mill for mixing and ball milling, and after ball milling is carried out for 1min, the obtained mixed powder is cooled to room temperature for later use; adjusting the pH value of the copper-containing wastewater to 5 by using alkali, adding 1g of mixed powder into 100ml of low-concentration copper-containing wastewater after the pH value is adjusted, stirring and reacting at 40 ℃ for 0.5h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting Cu in the copper-removed liquid2+The concentration was 0.43 ppm.
Example 3
The low-concentration copper-containing wastewater comes from a smelting plant, wherein the pH value of the wastewater is 5.5, and Cu is measured2+The concentration was 2 g/L. Firstly, putting 14g of metal aluminum powder and 6g of silicon dioxide particles into a vibration ball mill for mixing and ball milling, and after ball milling for 15min, cooling the obtained mixed powder to room temperature for later use; adding 1g of mixed powder into 200ml of low-concentration copper-containing wastewater, stirring at 50 ℃ for reaction for 2h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting to obtain Cu in the copper-removed liquid2+The concentration was 0.19 ppm.
Comparative example 1
Taking a low concentration copper containing waste water from the same smelter as example 3, wherein Cu is present2+The concentration was 2 g/L. Directly adding 1g of metal aluminum powder into 200ml of low-concentration copper-containing wastewater, stirring at 50 ℃ for reaction for 2h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting to obtain Cu in the copper-removed liquid2+The concentration was 1.98 g/L.
Comparative example 2
The low-concentration copper-containing waste water to be treated likewise corresponds to example 3. Uniformly mixing 14g of metal aluminum powder and 6g of silicon dioxide to obtain mixed powder, adding 1g of the mixed powder into 200ml of low-concentration copper-containing wastewater, stirring at 50 ℃ for reaction for 2h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting Cu in the copper-removed liquid2+The concentration was 1.99 g/L.
Comparative example 3
The low-concentration copper-containing waste water to be treated likewise corresponds to example 3. Firstly, putting 14g of metal aluminum powder and 6g of silicon dioxide particles into a vibration ball mill for mixing and ball milling, and after ball milling for 15min, cooling the obtained mixed powder to room temperature for later use; adding 1g of mixed powder into 200ml of low-concentration copper-containing wastewater, stirring at 20 ℃ for reaction for 2h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting to obtain Cu in the copper-removed liquid2+The concentration was 10 ppm.
Comparative example 4
The low-concentration copper-containing wastewater to be treated was the same as in example 2, i.e., the pH and copper ion concentration of the copper-containing wastewater were the same as those of the wastewater to be treated in example 2. Firstly, 18g of metal aluminum powder and 2g of silicon dioxide particles are put into a vibration ball mill for mixing and ball milling, and after ball milling is carried out for 1min, the obtained mixed powder is cooled to room temperature for later use; adding 1g of mixed powder into 100ml of low-concentration copper-containing wastewater without pH value adjustment, stirring and reacting at 40 ℃ for 0.5h, filtering to obtain copper-containing slag and copper-removed liquid, and detecting to obtain Cu in the copper-removed liquid2+The concentration was 8 ppm.
In conclusion, the Al/SiO is obtained by grinding2Mixing the powders and then based on Al/SiO2High reactivity of the mixed powder to Cu in copper-containing wastewater2+Act so that Cu2+The copper ions in the treated wastewater are less than 0.5ppm, so that the copper ions in the wastewater are deeply removed, and the requirement of direct discharge of water pollutants in GB25467-2010 on the concentration of total copper is completely met; and the whole copper removal process flow is short, the operation is simple, and the industrial application is easy.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. A method for treating low-concentration copper-containing wastewater is characterized by comprising the following steps:
1) uniformly mixing metal aluminum powder and silicon dioxide particles, and then grinding to obtain mixed powder; the mass ratio of the metal aluminum powder to the silicon dioxide particles is 1: 1-9: 1; the grinding is specifically grinding in a vibration ball mill for 1-15 min;
2) adjusting the pH value of the copper-containing wastewater to 5-9, adding the mixed powder obtained in the step 1), stirring for reaction, and carrying out solid-liquid separation to obtain copper-containing slag and a copper-removed liquid; cu in the copper-containing wastewater2+The concentration of (b) is 0.1-2 g/L.
2. The method for treating low-concentration copper-containing wastewater according to claim 1, wherein in the step 2), the mass-to-volume ratio of the mixed powder to the copper-containing wastewater is 0.1-1 g: 100 ml.
3. The method for treating low-concentration copper-containing wastewater according to claim 1, wherein in the step 2), the temperature of the stirring reaction is 25-50 ℃, and the time of the stirring reaction is 0.5-2 h.
4. The method for treating low-concentration copper-containing wastewater according to claim 1, wherein in the step 2), Cu in the copper-removed solution is2+Is less than 0.5 ppm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910982400.XA CN110759521B (en) | 2019-10-16 | 2019-10-16 | Method for treating low-concentration copper-containing wastewater |
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| CN201910982400.XA CN110759521B (en) | 2019-10-16 | 2019-10-16 | Method for treating low-concentration copper-containing wastewater |
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| CN110759521B true CN110759521B (en) | 2020-09-25 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009015413A1 (en) * | 2009-03-27 | 2010-09-30 | B.P.S. Engineering Gesellschaft für Umwelt und Automatisierungstechnik mbH | Adsorbent to remove heavy metals from contaminated water, comprises mesoporous material with homogeneous distribution containing metal oxides and high-molecular cationic polymers, which contain quaternary ammonium and/or phosphonium groups |
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| CN103304068A (en) * | 2013-07-03 | 2013-09-18 | 上海丰信环保科技有限公司 | Method for removing low-concentration copper-containing wastewater |
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