CN107459179B - Treatment method of wastewater generated in aluminum product processing - Google Patents
Treatment method of wastewater generated in aluminum product processing Download PDFInfo
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F2001/007—Processes including a sedimentation step
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- 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
- C02F2101/101—Sulfur 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention relates to the technical field of aluminum product processing, and discloses a method for treating wastewater generated in aluminum product processing, which comprises the steps of firstly measuring the concentration content of each ion in the wastewater, then adopting different treatment methods aiming at different ions, firstly removing aluminum ions contained in the wastewater, wherein the removal rate reaches more than 99.8%, then simultaneously removing sulfate ions and phosphate ions, saving the using amount of reagents, being simple to operate, having less residual sludge, not generating secondary pollution, reducing the cost by more than 20%, and finally treating heavy metal ions, wherein the heavy metal content in a treatment solution can be controlled to be far lower than the standard discharge amount.
Description
Technical Field
The invention belongs to the technical field of aluminum product processing, and particularly relates to a method for treating wastewater generated in aluminum product processing.
Background
Aluminum is a good energy-saving and environment-friendly material, and more aluminum products are used in industries such as building, packaging and transportation. The surface treatment of the aluminum is an indispensable procedure for producing aluminum products, the procedure has large water consumption, can generate a large amount of wastewater, has complex wastewater components and contains a large amount of A13+，S04 2-，Cr6+，Cr3+，F-，PO4 3-And the like, if left untreated, can severely pollute the environment. The surface treatment is to improve the corrosion resistance of the aluminum profile. The surface treatment is a crucial link in the aluminum profile manufacturing, and the link can not only improve the corrosion resistance of the aluminum profile, prolong the service life of the aluminum profile, but also expand the use range of the aluminum profile. Degreasing is also called as oil removal, namely removing pollutants such as rust removing oil and lubricating oil on the surface of the aluminum, and ensuring that the surface of the aluminum can be corroded uniformly during alkaline cleaning. The solvent used for degreasing is a surfactant, an organic solvent, an acidic solvent and the like. The wastewater generated in the degreasing process is acidic grease wastewater, and contains a degreasing agent and sulfuric acid. And (3) further removing pollutants on the surface of the aluminum through alkali liquor in alkaline washing, so that a natural oxide film on the surface of the aluminum is completely removed, a metal matrix is exposed, and subsequent anodic oxidation is conveniently carried out. The amount of aluminum dissolved in the alkali washing process is higherThe waste water generated is mainly alkaline aluminum-containing waste water.
In order to prevent the ecological environment from being damaged and ensure the quality of the aluminum profile, the wastewater must be treated to reach the discharge standard on the premise of ensuring that the life quality of human beings and the economic benefit of industry are not influenced. At present, the research on the wastewater generated by processing aluminum products is mostly limited to removing a single ion, and the treatment method is single, so that the problems of large medicament dosage, long reaction time, complex operation, more residual sludge, secondary pollution, high cost and the like exist, and the aim of harmless discharge of the wastewater cannot be really achieved.
Disclosure of Invention
The invention aims to solve the existing problems and provides a method for treating wastewater generated in aluminum product processing, the wastewater generated in the aluminum product processing is subjected to quality-based treatment, different treatment methods are adopted for different ions, the pertinence is strong, the treatment effect is good, the operation is simple, the equipment is simple, and the wastewater can reach the standard and be discharged.
The invention is realized by the following technical scheme:
a treatment method of waste water generated in aluminum product processing comprises the steps of firstly measuring the concentration content of each ion in the waste water, and then adopting different treatment methods aiming at different ions, and specifically comprises the following steps:
(1) the optimal process conditions for treating the aluminum ions are as follows: firstly, adding sodium hydroxide powder into the sewage, regulating pH value of system to 8.5-9.0, heating to 50-60 deg.C, then adding (NH) whose concentration is 3-4 times of aluminium ion concentration in the sewage4)2SO4The solution reacts under stirring, after the reaction is finished, the solution is cooled to 20-25 ℃, and after crystallization, the solution is filtered to remove aluminum ions;
(2) the optimal process conditions for treating sulfate ions and phosphate ions are as follows: firstly, adding calcium oxide powder into sewage, adjusting the pH value of the system to be within the range of 7.5-7.8, then adding a porous adsorbent accounting for 0.1-0.2% of the volume fraction of the sewage, stirring and reacting for 8-10min, placing the mixture into a constant-temperature stirring water bath kettle, stirring until brown flocculent colloid particles are formed, stopping stirring, cooling to 15-20 ℃, standing for 20-25min, and filtering;
(3) the optimal process conditions for treating the chromium ions are as follows: firstly, sulfuric acid solution is used for regulating the pH value of oxidation-reduction stage to 6.5-6.8, then reducing agent FeSO whose concentration is 3-5 times that of chromium ion is added4·7H2And O, reacting for 4-6min after uniformly stirring, adjusting the pH value of the coprecipitation stage to be 7.2-7.3 by using ammonia water, placing the coprecipitation system in a constant-temperature stirring water bath kettle for stirring until a dark brown precipitate is generated, stopping stirring until the precipitate is not generated, reacting until the precipitate is not generated, cooling to 15-20 ℃, standing for 30-40min, and filtering.
As a further improvement to the scheme, the reaction time in the step (1) is 4-6h, and the stirring speed is 60-80 r/min.
As a further improvement to the scheme, the calcium oxide powder is added in the step (2) in an amount which is 1-2 times of the total concentration of sulfate ions and phosphate ions according to the concentration of calcium ions, the porous adsorbent contains 20-30% of polyaluminum chloride, 10-20% of fly ash and the balance of silicon nitride ceramic powder, and the particle size range of the porous adsorbent is 180-200 meshes.
As a further improvement of the scheme, the concentration of the sulfuric acid solution used in the step (3) is 4-6 mol/L, the concentration of ammonia water is 8-10 mol/L, and the temperature in a constant-temperature water bath kettle is 60-70 ℃.
Compared with the prior art, the invention has the following advantages: in order to solve the problem of improper treatment mode of the waste water generated in the processing of the aluminum products, the invention provides a treatment method of the waste water generated in the processing of the aluminum products, firstly, the concentration content of each ion in the waste water is measured, then different treatment methods are adopted aiming at different ions, firstly, the aluminum ions contained in the sewage are removed, the removal rate reaches more than 99.8 percent, the method has the advantages that the sulfate ions and the phosphate ions are simultaneously removed, the using amount of reagents is saved, the operation is simple, the residual sludge is less, the secondary pollution is avoided, the cost is reduced by more than 20%, finally, the heavy metal ions are treated, the heavy metal content in the treatment liquid can be controlled to be far lower than the standard discharge amount, the wastewater generated in the aluminum product processing is subjected to quality-based treatment, the pertinence is strong, the treatment effect is good, the operation is simple, the equipment is simple, and the wastewater can be discharged after reaching the standard.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A treatment method of waste water generated in aluminum product processing comprises the steps of firstly measuring the concentration content of each ion in the waste water, and then adopting different treatment methods aiming at different ions, and specifically comprises the following steps:
(1) the optimal process conditions for treating the aluminum ions are as follows: firstly, adding sodium hydroxide powder into the sewage, regulating the pH value of the system to be 8.5-9.0, heating to 50 ℃, and then adding (NH) with the concentration 3 times of that of aluminum ions in the sewage4)2SO4The solution reacts under stirring, after the reaction is finished, the solution is cooled to 20 ℃, and after crystallization, the solution is filtered to remove aluminum ions;
(2) the optimal process conditions for treating sulfate ions and phosphate ions are as follows: firstly, adding calcium oxide powder into sewage, adjusting the pH value of a system to be within the range of 7.5-7.8, then adding a porous adsorbent accounting for 0.1% of the volume fraction of the sewage, stirring and reacting for 8min, placing the mixture into a constant-temperature stirring water bath kettle, stirring until brown flocculent colloid particles are formed, cooling to 15 ℃, standing for 20min, and filtering;
(3) the optimal process conditions for treating the chromium ions are as follows: firstly, sulfuric acid solution is used for regulating the pH value of an oxidation-reduction stage to be 6.5-6.8, and then reducing agent FeSO with the concentration 3 times that of chromium ions is added4·7H2And O, reacting for 4min after uniformly stirring, adjusting the pH value of the coprecipitation stage to be within the range of 7.2-7.3 by using ammonia water, placing the coprecipitation system in a constant-temperature stirring water bath kettle for stirring until a dark brown precipitate is generated, stopping stirring until the precipitate is not generated, reacting until the precipitate is not generated, cooling to 15 ℃, standing for 30min, and filtering.
As a further improvement to the above scheme, the reaction time in step (1) is 4h, and the stirring speed is 60 r/min.
As a further improvement to the scheme, the calcium oxide powder is added in the step (2) in an amount which is 1 time of the total concentration of sulfate ions and phosphate ions according to the concentration of calcium ions, the porous adsorbent contains 20% of polyaluminium chloride, 10% of fly ash and the balance of silicon nitride ceramic powder, and the particle size range of the porous adsorbent is 180-200 meshes.
As a further improvement to the above scheme, the concentration of the sulfuric acid solution used in step (3) is 4 mol/liter, the concentration of ammonia water is 8 mol/liter, and the temperature in the constant temperature water bath is 60 ℃.
Example 2
A treatment method of waste water generated in aluminum product processing comprises the steps of firstly measuring the concentration content of each ion in the waste water, and then adopting different treatment methods aiming at different ions, and specifically comprises the following steps:
(1) the optimal process conditions for treating the aluminum ions are as follows: firstly, adding sodium hydroxide powder into the sewage, regulating the pH value of the system to be 8.5-9.0, heating to 55 ℃, and then adding (NH) with the concentration 3.5 times of that of aluminum ions in the sewage4)2SO4The solution reacts under stirring, after the reaction is finished, the solution is cooled to 23 ℃, and after crystallization, the solution is filtered to remove aluminum ions;
(2) the optimal process conditions for treating sulfate ions and phosphate ions are as follows: firstly, adding calcium oxide powder into sewage, adjusting the pH value of a system to be within the range of 7.5-7.8, then adding a porous adsorbent accounting for 0.15% of the volume fraction of the sewage, stirring and reacting for 9min, placing the mixture into a constant-temperature stirring water bath kettle, stirring until brown flocculent colloid particles are formed, cooling to 19 ℃, standing for 22min, and filtering;
(3) the optimal process conditions for treating the chromium ions are as follows: firstly, sulfuric acid solution is used for regulating the pH value of an oxidation-reduction stage to be 6.5-6.8, and then reducing agent FeSO with the concentration 4 times that of chromium ions is added4·7H2And O, reacting for 5min after uniformly stirring, adjusting the pH value of the coprecipitation stage to be within the range of 7.2-7.3 by using ammonia water, placing the coprecipitation system in a constant-temperature stirring water bath kettle for stirring until a dark brown precipitate is generated, stopping stirring, reacting until the precipitate is not generated, cooling to 18 ℃, standing for 35min, and filtering.
As a further improvement to the scheme, the reaction time in the step (1) is 5h, and the stirring speed is 70 r/min.
As a further improvement to the scheme, the calcium oxide powder is added in the step (2) according to the calcium ion concentration of 1.5 times of the total concentration of sulfate ions and phosphate ions, the porous adsorbent contains 25% of polyaluminium chloride, 15% of fly ash and the balance of silicon nitride ceramic powder, and the particle size range of the porous adsorbent is 180-200 meshes.
As a further improvement to the above-mentioned protocol, the sulfuric acid solution used in step (3) had a concentration of 5 mol/liter, the aqueous ammonia concentration of 9 mol/liter, and the temperature in the thermostatic waterbath was 65 ℃.
Example 3
A treatment method of waste water generated in aluminum product processing comprises the steps of firstly measuring the concentration content of each ion in the waste water, and then adopting different treatment methods aiming at different ions, and specifically comprises the following steps:
(1) the optimal process conditions for treating the aluminum ions are as follows: firstly, adding sodium hydroxide powder into the sewage, regulating the pH value of the system to be 8.5-9.0, heating to 60 ℃, and then adding (NH) with the concentration 4 times of that of aluminum ions in the sewage4)2SO4The solution reacts under stirring, after the reaction is finished, the solution is cooled to 25 ℃, and after crystallization, the solution is filtered to remove aluminum ions;
(2) the optimal process conditions for treating sulfate ions and phosphate ions are as follows: firstly, adding calcium oxide powder into sewage, adjusting the pH value of a system to be within the range of 7.5-7.8, then adding a porous adsorbent accounting for 0.2% of the volume fraction of the sewage, stirring and reacting for 10min, placing the mixture into a constant-temperature stirring water bath kettle, stirring until brown flocculent colloid particles are formed, cooling to 20 ℃, standing for 25min, and filtering;
(3) the optimal process conditions for treating the chromium ions are as follows: firstly, sulfuric acid solution is used for regulating the pH value of an oxidation-reduction stage to be 6.5-6.8, and then reducing agent FeSO with the concentration 5 times that of chromium ions is added4·7H2O, reacting for 6min after being stirred uniformly, adjusting the pH value of the coprecipitation stage to be 7.2-7.3 by ammonia water, placing the coprecipitation system at constant temperature and stirringStirring in water bath until dark brown precipitate is generated, stopping stirring, reacting until precipitate is not generated, cooling to 20 deg.C, standing for 40min, and filtering.
As a further improvement to the scheme, the reaction time in the step (1) is 6h, and the stirring speed is 80 r/min.
As a further improvement to the scheme, the calcium oxide powder is added in the step (2) in an amount which is 1-2 times of the total concentration of sulfate ions and phosphate ions according to the concentration of calcium ions, the porous adsorbent contains 30% of polyaluminum chloride, 20% of fly ash and the balance of silicon nitride ceramic powder, and the particle size range of the porous adsorbent is 180-200 meshes.
As a further improvement to the above-mentioned scheme, the concentration of the sulfuric acid solution used in step (3) is 6 mol/liter, the concentration of ammonia water is 10 mol/liter, and the temperature in the thermostatic waterbath is 70 ℃.
Comparative example 1
The only difference from example 1 is that the removal of aluminium ions is put to the last step, the rest remaining consistent.
Comparative example 2
The only difference from example 2 is that the sulfate ions are removed separately from the phosphate ions, and the rest remains the same.
Comparative example 3
The difference from example 3 is only that the treatment process of the porous adsorbent in step (3) is omitted and the rest is kept in agreement.
Comparative experiment
The wastewater generated in the aluminum product processing is treated by the methods of examples 1-3 and comparative examples 1-3, respectively, and the same wastewater sample is treated by the existing aluminum product wastewater treatment method as a control, and the treatment results of each group are recorded as shown in the following table:
| item | A13+Recovery (%) | Cr6+ Concentration (mg/L) | PO4 3-Concentration (mg/L) | SO4 2-Concentration (mg/L) |
| Example 1 | 99.8 | 0.08 | 0.15 | 12.5 |
| Example 2 | 99.9 | 0.06 | 0.13 | 12.2 |
| Example 3 | 99.9 | 0.07 | 0.14 | 12.3 |
| Comparative example 1 | 92.5 | 0.15 | 0.41 | 40.6 |
| Comparative example 2 | 95.6 | 0.17 | 0.78 | 73.5 |
| Comparative example 3 | 94.9 | 0.46 | 0.42 | 41.3 |
| Control group | 92.1 | 0.58 | 0.82 | 74.6 |
It can be seen from this that: the invention carries out quality-based treatment on the wastewater generated in the aluminum product processing, has strong pertinence, good treatment effect, simple operation and simple equipment, and the wastewater can reach the discharge standard.
Claims (4)
1. A treatment method of waste water generated in aluminum product processing is characterized in that the concentration content of each ion in the waste water is firstly measured, and then different treatment methods are adopted aiming at different ions, and the method specifically comprises the following steps:
(1) in the first step, aluminum ions are processed: firstly, adding sodium hydroxide powder into the sewage, regulating pH value of system to 8.5-9.0, heating to 50-60 deg.C, then adding (NH) whose concentration is 3-4 times of aluminium ion concentration in the sewage4)2SO4The solution reacts under stirring, after the reaction is finished, the solution is cooled to 20-25 ℃, and after crystallization, the solution is filtered to remove aluminum ions;
(2) step two, treating sulfate ions and phosphate ions: firstly, adding calcium oxide powder into sewage, adjusting the pH value of the system to be within the range of 7.5-7.8, then adding a porous adsorbent accounting for 0.1-0.2% of the volume fraction of the sewage, stirring and reacting for 8-10min, placing the mixture into a constant-temperature stirring water bath kettle, stirring until brown flocculent colloid particles are formed, stopping stirring, cooling to 15-20 ℃, standing for 20-25min, and filtering;
(3) step three, processing chromium ions: firstly, sulfuric acid solution is used for regulating the pH value of oxidation-reduction stage to 6.5-6.8, then reducing agent FeSO whose concentration is 3-5 times that of chromium ion is added4·7H2And O, reacting for 4-6min after uniformly stirring, adjusting the pH value of the coprecipitation stage to be 7.2-7.3 by using ammonia water, placing the coprecipitation system in a constant-temperature stirring water bath kettle for stirring until a dark brown precipitate is generated, stopping stirring until the precipitate is not generated, reacting until the precipitate is not generated, cooling to 15-20 ℃, standing for 30-40min, and filtering.
2. The method according to claim 1, wherein the treatment of the waste water generated in the processing of the aluminum product,
the reaction time in the step (1) is 4-6h, and the stirring speed is 60-80 r/min.
3. The method according to claim 1, wherein the treatment of the waste water generated in the processing of the aluminum product,
the addition amount of the calcium oxide powder in the step (2) is 1-2 times of the total concentration of sulfate ions and phosphate ions according to the concentration of calcium ions, the porous adsorbent contains 20-30% of polyaluminium chloride, 10-20% of fly ash and the balance of silicon nitride ceramic powder, and the particle size range of the porous adsorbent is 180-200 meshes.
4. The method according to claim 1, wherein the treatment of the waste water generated in the processing of the aluminum product,
the concentration of the sulfuric acid solution used in the step (3) is 4-6 mol/L, the concentration of ammonia water is 8-10 mol/L, and the temperature in a constant-temperature water bath kettle is 60-70 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293717A (en) * | 2008-06-05 | 2008-10-29 | 佛山市三水凤铝铝业有限公司 | Method for processing and recycling wastewater containing fluorine, chromium ion |
| US20130001173A1 (en) * | 2010-03-10 | 2013-01-03 | Sumitomo Mental Mining Co., Ltd. | Method for a treatment for wastewater containing aluminum, magnesium, and manganese |
| CN104609615A (en) * | 2015-02-13 | 2015-05-13 | 江苏艾特克环境工程设计研究院有限公司 | Heavy-metal-containing surface treatment wastewater treatment method |
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| CN101293717A (en) * | 2008-06-05 | 2008-10-29 | 佛山市三水凤铝铝业有限公司 | Method for processing and recycling wastewater containing fluorine, chromium ion |
| US20130001173A1 (en) * | 2010-03-10 | 2013-01-03 | Sumitomo Mental Mining Co., Ltd. | Method for a treatment for wastewater containing aluminum, magnesium, and manganese |
| CN104609615A (en) * | 2015-02-13 | 2015-05-13 | 江苏艾特克环境工程设计研究院有限公司 | Heavy-metal-containing surface treatment wastewater treatment method |
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