CN103588325A - Acid pickling phosphorization industrial wastewater regenerating cycle method - Google Patents
Acid pickling phosphorization industrial wastewater regenerating cycle method Download PDFInfo
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- CN103588325A CN103588325A CN201310592976.8A CN201310592976A CN103588325A CN 103588325 A CN103588325 A CN 103588325A CN 201310592976 A CN201310592976 A CN 201310592976A CN 103588325 A CN103588325 A CN 103588325A
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Abstract
The invention relates to an acid pickling phosphorization industrial wastewater regenerating cycle method and belongs to the field of metal surface treatment and environmental protection. According to the invention, 'the agentia floating method' and 'the secondary sedimentation separation method' are mainly adopted to perform oil-water separation and heavy metal sedimentation separation on wastewater generated through acid pickling phosphorization, the obtained oil and heavy metallic salt are handed over to a unit designated by the environmental protection agency for conversion and utilization, and the filtered clear water can be recycled to be applicable to the production process. The acid pickling phosphorization industrial wastewater regenerating cycle method is a novel technique applicable to cleaner production and acid pickling phosphorization processing, saves water from the source, fulfills energy conservation and emission reduction, and reduces cost.
Description
Technical field
The present invention relates to the method for recycling of acid washing phosphorization trade effluent, belong to metal finishing and field of Environment Protection.
Background technology
Acid washing phosphorization processing industry is metal processing manufacturing industry, paint industry, weaponry production and aerospace application technique very widely.Mainly contain oil removing, rust cleaning, phosphatization, turn blue, the operation such as antirust, passivation, for guaranteeing to enter the clean-up performance of next procedure metallic element, between every procedure, have water for cleaning, so the sector produces a large amount of trade effluents.
1, the antirust processing typical process of pickling:
Oil removing → washing → rust cleaning → washing → antirust → dry (or dewatering rust preventive oil)
2, metal phosphorizing processing typical process:
Oil removing → washing → rust cleaning → washing → table tune → phosphatization → hot water wash (being dried)
3, metal bluing (blackout) processing typical process:
Oil removing → washing → rust cleaning → washing → turning blue (blackout) → hot water wash → washing → washing → dry → dewatering rust preventive oil
Traditional technology is by trade effluent centralized collection, carries out neutralizing treatment, qualified discharge.Or pay effluent charge, be handed over to Environmental Protection Agency and specify sewage work to process.Not only waste water resource but also increase enterprise cost.
Acid washing phosphorization waste water is mainly containing Zn
2+, Mn
2+, Ni
2+, Ca
2+, Cr
2+, Cu
2+, PO
4 3-, NO
3 -, NO
2 -, Cl
-and SO
4 2-plasma, major part can precipitate and separate under alkaline condition for above-mentioned heavy metal ion, the heavy metal after recovery can trans-utilization, the clear water after regeneration can cycle applications in Production Flow Chart.
Summary of the invention
The object of the invention is to overcome the deficiency that produces a large amount of waste water in acid washing phosphorization process, a kind of method for recycling of trade effluent is provided, the method is the novel process that meets energy-saving and emission-reduction and acid washing phosphorization technical requirements, can make the waste water producing in production process obtain reprocessing cycle use, save water resources, reduce enterprise cost.
The present invention mainly adopts " medicament floating method " and " secondary settlement partition method ", it is settlement separate that the waste water that acid washing phosphorization is produced carries out respectively oily water separation and heavy metal, the oil obtaining and heavy metallic salt are handed over to Environmental Protection Agency and specify unit conversion utilization, the clear water after filtration can cycle applications in Production Flow Chart.The method is a kind of new process that meets cleaner production and acid washing phosphorization processing, and from source water saving, energy-saving and emission-reduction, reduce costs.The present invention is achieved through the following technical solutions.
The method for recycling of acid washing phosphorization trade effluent, is characterized in that, comprises the following steps:
In described step 1, step 3, described pond for recovering will be done antiseepage and process.
Oil after described oily water separation is handed over to Environmental Protection Agency and specifies unit centralized recovery utilization.
In described step 3, waste water pH value and Zn in described detection pond for recovering
2+, Mn
2+, Ni
2+, Ca
2+, Cr
2+, Cu
2+, PO
4 3-, NO
3 -, NO
2 -, Cl
-, SO
4 2-the method of ion content is described in chemical analysis and atomic absorption in step 4, and described alkaline assistant comprises: sodium hydroxide, potassium hydroxide, unslaked lime, calcium hydroxide.
In described step 4, the fractional dose of described coagulation water metal ion is greater than 90%; The Ph > 10 of described coagulation water.
Described first grade subsides is separated, and the heavy metal sediment obtaining is handed over to Environmental Protection Agency and specifies unit centralized recovery utilization.
In described step 5, described acid is hydrochloric acid or nitric acid.
invention beneficial effect:the present invention has overcome technically and in the acid washing phosphorization course of processing, has produced a large amount of waste water.Adopt " medicament floating method " and " secondary settlement partition method " can realize in production scene the comprehensive utilization of waste water.Isolate waste oil and heavy metal centralized recovery recycling, the clear water cycle applications obtaining is in Production Flow Chart, and energy-saving and emission-reduction, reduce costs, and benefit the society.
Accompanying drawing explanation
Fig. 1 is acid washing phosphorization trade effluent reprocessing cycle schema.
Embodiment
1, the antirust processing typical process of pickling:
Oil removing → 1. washing → rust cleaning → 3. washing → antirust → dry (or it is antirust to dewater)
2, metal phosphorizing processing typical process:
The hot water wash (being dried) of the washing → table tune → phosphatization of the washing → rust cleaning of oil removing → 1. → 3. → 3.
3, metal bluing (blackout) processing typical process:
Oil removing → 1. washing → rust cleaning → 3. wash → turn blue (blackout) → 1. hot water wash → 1. washing → 1. wash → be dried → dewatering rust preventive oil
Schema of the present invention is shown in Fig. 1: acid washing phosphorization trade effluent reprocessing cycle schema
1, classification of waste is collected: the wastewater collection being labeled as on above-mentioned three production lines is 1. arrived to 1# pond for recovering; The Cleaning Wastewater being labeled as is 3. collected 3# pond for recovering;
2, medicament floating method: detect 1# waste water greasy dirt degree and Ph value, upper strata oil slick is salvaged to waste oil groove; 1# pond for recovering water is pumped into 2# pond for recovering, add appropriate flocculation agent (PAM or PAC), realize oily water separation, isolated oil is collected waste oil groove;
3, detect and analyze:
Detect the content of 3# pond for recovering metal and nonmetallic ion.Zn
2+1.97mg/L, Ca
2+1.31mg/L, Mn
2+0.83 mg/L, Ni
2+0.011 mg/L, PO
4 3-2.83mg/L, SO
4 2-1.52mg/L; Ph value 3.1.
4, one-level water treatment: 2# and 3# pond for recovering water are pumped into 1# neutralization tank, add alkaline conditioner (sodium hydroxide, potassium hydroxide, calcium oxide or calcium hydroxide), regulate waste water Ph value > 10.0, produce throw out in pond for recovering.Filter, sediment after filtration is deposited in to heavy metal salt bath, the clear water obtaining is coagulation water, pumps into 2# neutralization tank.
5, secondary water treatment: coagulation water is neutralized, add appropriate acid regulator (hydrochloric acid or nitric acid), regulate Ph value to 6.5.Adopt membrane technique to carry out filtering separation, obtaining clear water is secondary treated wastewater.Filter residue is put into heavy metal salt bath;
6, quality monitoring: secondary treated wastewater is detected to analysis, total zinc 0.041mg/L, total manganese 0.018mg/L, total phosphorus 0.67mg/L.
7, reprocessing cycle system: above-mentioned secondary clear water is stored in to middle pond, and cycle applications is processed cleaning process in phosphatization.
Described pond for recovering will be done antiseepage and process.
Described detection pond for recovering waste water Zn
2+, Mn
2+, Ni
2+, Ca
2+, PO
4 3-and SO
4 2-ion content method is chemical analysis and atomic absorption spectrophotometry.
The separation of metal ions amount of described coagulation water is greater than 90%; Described Ph > 8.5.
Described acid is hydrochloric acid or nitric acid.
The above; it is only preferably embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; according to technical scheme of the present invention and inventive concept thereof, be equal to replacement or changed, within all should being encompassed in protection scope of the present invention.
Claims (8)
1. the method for recycling of acid washing phosphorization trade effluent, is characterized in that, comprises the following steps:
Step 1, the alkaline waste water that acid washing phosphorization processing is produced are collected in 1# pond for recovering, detect waste water greasy dirt degree and Ph value, and upper strata oil slick is salvaged and reclaimed;
Step 2, the waste water of 1# pond for recovering is pumped into 2# pond for recovering, adopt " medicament floating method ", realize oily water separation;
Step 3, the acid waste water that acid washing phosphorization processing is produced are collected in 3# pond for recovering, analyze Zn
2+, Mn
2+, Ni
2+, Ca
2+, Cr
2+, Cu
2+, PO
4 3-, NO
3 -, NO
2 -, Cl
-and SO
4 2-ion content, detects Ph value;
Step 4, the water of 2#, 3# pond for recovering is pumped into 1# neutralization tank, add alkali to regulate Ph value > 10, waste water is carried out to first grade subsides separation, the clear water obtaining is coagulation water;
Step 5, coagulation water is pumped into 2# neutralization tank, add acid to regulate Ph value 6.5～8.5, employing membrane technique carries out filtering separation, and the clear water obtaining is secondary treated wastewater;
Step 6, secondary treated wastewater is detected to analysis, monitor total zinc, total manganese, total phosphorous, total zinc < 0.05mg, total manganese < 0.05mg/L, total phosphorus < 1.0mg/L, secondary treated wastewater is stored in to middle pond, this water can cycle applications in the cleaning process flow of metal phosphorizing processing, do not affect product quality and performances.
2. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, in described step 1, step 3, described pond for recovering will be done antiseepage and process.
3. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, the oil after described oily water separation is handed over to Environmental Protection Agency and specifies unit centralized recovery utilization.
4. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, in described step 3, and waste water pH value and Zn in described detection pond for recovering
2+, Mn
2+, Ni
2+, Ca
2+, Cr
2+, Cu
2+, PO
4 3-, NO
3 -, NO
2 -, Cl
-, SO
4 2-the method of ion content is chemical analysis and atomic absorption spectrophotometry.
5. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, in described step 4, described alkaline assistant comprises: sodium hydroxide, potassium hydroxide, unslaked lime, calcium hydroxide.
6. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, in described step 4, the fractional dose of described coagulation water metal ion is greater than 90%; The Ph > 10 of described coagulation water.
7. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, described first grade subsides is separated, and the heavy metal sediment obtaining is handed over to Environmental Protection Agency and specifies unit centralized recovery utilization.
8. the method for recycling of acid washing phosphorization trade effluent according to claim 1, is characterized in that, in described step 5, described acid is hydrochloric acid or nitric acid.
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| CN201310592976.8A CN103588325A (en) | 2013-11-22 | 2013-11-22 | Acid pickling phosphorization industrial wastewater regenerating cycle method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673304A (en) * | 2016-12-19 | 2017-05-17 | 徐州工程学院 | Device for treating phosphatized wastewater through biological reaction and working method thereof |
| CN108793592A (en) * | 2018-06-07 | 2018-11-13 | 四川旭昊德环保设备有限公司 | A kind of Industrial sewage treatment system |
Citations (3)
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|---|---|---|---|---|
| CN1498193A (en) * | 2000-11-15 | 2004-05-19 | �����ɷ� | Treatment of nickel-containing waste water on phosphating |
| CN201330204Y (en) * | 2008-03-14 | 2009-10-21 | 许建民 | Device for water conservation as well as pollutant and consumption reduction applied in the coating pre-treatment parkerizing process |
| WO2012098924A1 (en) * | 2011-01-20 | 2012-07-26 | 三菱レイヨン株式会社 | Wastewater treatment apparatus, wastewater treatment method, and wastewater treatment system |
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2013
- 2013-11-22 CN CN201310592976.8A patent/CN103588325A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498193A (en) * | 2000-11-15 | 2004-05-19 | �����ɷ� | Treatment of nickel-containing waste water on phosphating |
| CN201330204Y (en) * | 2008-03-14 | 2009-10-21 | 许建民 | Device for water conservation as well as pollutant and consumption reduction applied in the coating pre-treatment parkerizing process |
| WO2012098924A1 (en) * | 2011-01-20 | 2012-07-26 | 三菱レイヨン株式会社 | Wastewater treatment apparatus, wastewater treatment method, and wastewater treatment system |
Non-Patent Citations (1)
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|---|
| 刘永等: "冰箱行业酸洗磷化污水除磷工艺研究", 《合肥工业大学学报(自然科学版)》, vol. 21, no. 1, 28 February 1998 (1998-02-28), pages 81 - 84 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673304A (en) * | 2016-12-19 | 2017-05-17 | 徐州工程学院 | Device for treating phosphatized wastewater through biological reaction and working method thereof |
| CN108793592A (en) * | 2018-06-07 | 2018-11-13 | 四川旭昊德环保设备有限公司 | A kind of Industrial sewage treatment system |
| CN108793592B (en) * | 2018-06-07 | 2021-10-22 | 四川纯阳润森节能环保有限公司 | Industrial sewage treatment system |
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Application publication date: 20140219 |