CN1340466A - Process for treating waste industrial phosphorizing liquid - Google Patents
Process for treating waste industrial phosphorizing liquid Download PDFInfo
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- CN1340466A CN1340466A CN 00122933 CN00122933A CN1340466A CN 1340466 A CN1340466 A CN 1340466A CN 00122933 CN00122933 CN 00122933 CN 00122933 A CN00122933 A CN 00122933A CN 1340466 A CN1340466 A CN 1340466A
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Abstract
A process for treaitng the waste industrial phosphorizing liquid includes such steps as educing out Fe, educing out heavy metals, adding transforming agent, stirring and evaporating, then separating out P-K compound, N-K compound and P-N compound, and preparing nickel oxide and zinc oxide from educed-out heavy metals. Its advantages include use of waste prevention of "red tide" from occurring, and no secondary pollution.
Description
The present invention relates to a kind of treatment process of waste industrial phosphorizing liquid, particularly a kind of making generates the treatment process that product utilizes again.
At present, also there is not suitable treatment process for waste industrial phosphorizing liquid.For this reason, not treated just being discharged in the Nature of up to ten thousand tons of waste industrial phosphorizing liquids in domestic every year gone.Owing to contain a large amount of heavy metals, phosphorus and nitrogen in the useless phosphatization liquid, directly contaminate environment.And high-load phosphorus and nitrogen enter and can form the eutrophy district after the sea, then " red tide " can take place after it and inland sea warm current meet.In recent years, along with developing rapidly of industry, the generally use of phosphating process, waste industrial phosphorizing liquid discharges in a large number, coastal " red tide " of China also once taken place several times by 1 year by original generation decades, and " red tide " phenomenon proves absolutely that a large amount of discharging meetings of not treated waste industrial phosphorizing liquid bring serious consequence to the mankind.
The treatment process that the purpose of this invention is to provide a kind of waste industrial phosphorizing liquid is fundamentally stopped the pollution of useless phosphatization liquid to the Nature, eliminates offshore area " red tide " phenomenon.
Technical solution of the present invention is: a kind of treatment process of waste industrial phosphorizing liquid comprises the steps:
A. separate out the iron in the useless phosphatization liquid;
B. separate out the heavy metal in the useless phosphatization liquid;
C. in the useless phosphatization liquid of separating out heavy metal, add transforming agent, after stirring evaporation, separate phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound;
D. the heavy metal of being separated out with the b step is produced nickel oxide, zinc oxide.
Described a step is the iron-holder of the useless phosphatization liquid of chemical examination, press 1g iron/liter adding 1ml hydrogen peroxide according to result of laboratory test, add hydrogen peroxide in useless phosphatization liquid, making the pH value of useless phosphatization liquid with the ammoniacal liquor adjustment again is 2-3, make the iron precipitation, filter to isolate the iron ion in the useless phosphatization liquid.
Described b step is for to be mixed with treatment agent with alkali, ammonium hydroxide, flocculation agent and water; Weight proportion is alkali 20%-25%, ammonium hydroxide 6%-8%, flocculation agent 2%-4%, and other is a water; Add treatment agent 100-300Kg in the useless phosphatization liquid of every kilolitre, fully stir, the adjustment pH value is 8-9, makes the heavy metal ion precipitation, leaves standstill, filters.
Described alkali is potassium hydroxide or sodium hydroxide.
Described c step is that the ammoniacal liquor of 20-30% is transforming agent for add concentration in the useless phosphatization liquid of separating out heavy metal, constant-temperature evaporation after abundant stirring, with quarternary phase diagram separate phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound.
Add conversion rate promotor again after adding transforming agent.
Described d step is dissolved with acid for the heavy metal that the b step is separated out; Add alkali and make it to form precipitation, add alkali and heating again, filtering-depositing makes NiO through washing, drying and dewatering; Adding acid again in filtrate, to adjust pH value be 8.5, produces new precipitation, after filtration, washing, drying and dewatering make ZnO.
Described acid is phosphoric acid or nitric acid.
The present invention compared with prior art has following advantage:
1. the heavy metal in the waste industrial phosphorizing liquid, phosphorus and nitrogen are handled, avoided, the protection environment owing to materials such as the heavy metal in the waste liquid, phosphorus and nitrogen enter " red tide " phenomenon that produces in the Nature;
2. give up phosphatization liquid after treatment, the product of generation can synthesize new phosphatization liquid and composite fertilizer, reaches utilization of waste material;
3. the entire treatment process is simple, easy to operate, does not produce secondary pollution.
The present invention will be further described below in conjunction with embodiments of the invention:
Embodiment 1:a.Get 500 liters of waste industrial phosphorizing liquids, through the chemical examination iron-holder is the 4g/ liter, adds the 1ml hydrogen peroxide by every gram iron/every liter and calculates, and then should add concentration and be 30% hydrogen peroxide 2000ml in 500 liters of useless phosphatization liquid, be 30% ammoniacal liquor adding concentration then, stir while adding, measure pH value simultaneously, when pH value is 2, just stop to add ammoniacal liquor, iron precipitation in the at this moment useless phosphatization liquid is filtered, is separated, and removes the iron ion in the phosphatization liquid that gives up.
The chemical equation of this process is:
b。With potassium hydroxide, ammonium hydroxide, Wa-3 flocculation agent be by weight 20%, 6%, 2% all the other make useless phosphatization liquid treatment agent for the ratio of water, join with the useless phosphatization liquid treatment agent of 50 Kg earlier and remove in the useless phosphatization liquid of de-iron, fully stir, add useless phosphatization liquid treatment agent more gradually, measure pH value simultaneously, the adjustment pH value is 8-9, at this moment, heavy metal in the useless phosphatization liquid all precipitates, and leaves standstill more than 4 hours, filters throw out is separated.
The chemical equation of this process is:
c。In the solution of elimination heavy metal, add 10Kg concentration again and be 20% ammoniacal liquor as changing agent, fully stir, utilize constant-temperature evaporation, separate obtaining phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound with quarternary phase diagram.
d。At last, the throw out that filtration is obtained is handled.In throw out, add phosphoric acid and make the throw out dissolving, adding potassium hydroxide then makes it form precipitation, add excessive potassium hydroxide heating again, making the resolution of precipitate of zinc change into zincate is dissolved in the solution, nickel still exists in solution with precipitated form, precipitate after filtration, washing, drying and dewatering, can be made into NiO.Add phosphoric acid again in filtrate, adjusting pH value is 8.5, and zincate changed into Zn (OH) and was precipitated out again this moment, after filtration, washing, drying and dewatering obtain white ZnO.Gained filtrate can be done with the filtrate merging of b step gained and be extracted composite fertilizer's material phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound usefulness.
The chemical equation of this process is:
Embodiment 2:a.Get 1000 liters of waste industrial phosphorizing liquids, through the chemical examination iron-holder is the 10g/ liter, adds the ml hydrogen peroxide by every gram iron/every liter and calculates, and then should add concentration and be 30% hydrogen peroxide 10000ml in 1000 liters of useless phosphatization liquid, be 30% ammoniacal liquor adding concentration then, stir while adding, measure pH value simultaneously, when pH value is 3, just stop to add ammoniacal liquor, iron precipitation in the at this moment useless phosphatization liquid is filtered, is separated, and removes the iron ion in the phosphatization liquid that gives up.
b。With potassium hydroxide, ammonium hydroxide, Wa-3 flocculation agent be by weight 23%, 7%, 3% all the other for the ratio of water is mixed with useless phosphatization liquid treatment agent, join with the useless phosphatization liquid treatment agent of 200Kg earlier and remove in the useless phosphatization liquid of de-iron, fully stir, add useless phosphatization liquid treatment agent more gradually, measure pH value simultaneously, the adjustment pH value is 8-9, at this moment, heavy metal in the useless phosphatization liquid all precipitates, and leaves standstill more than 4 hours, filters throw out is separated.
c。In the solution of elimination heavy metal, add 20Kg concentration again and be 25% ammoniacal liquor as changing agent, for fast reaction speed, can to add concentration again be 2% Fx-3 promotor, fully stir, utilize constant-temperature evaporation, separate obtaining phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound with quarternary phase diagram.
d。At last, the throw out that filtration is obtained is handled.In throw out, add phosphoric acid and make the throw out dissolving, adding potassium hydroxide then makes it form precipitation, add excessive potassium hydroxide heating again, making the resolution of precipitate of zinc change into zincate is dissolved in the solution, nickel still exists in solution with precipitated form, precipitate after filtration, washing, drying and dewatering, can be made into NiO.Add phosphoric acid again in filtrate, adjusting pH value is 8.5, and zincate changed into Zn (OH) and was precipitated out again this moment, after filtration, washing, drying and dewatering obtain white ZnO.Gained filtrate can be done with the filtrate merging of b step gained and be extracted composite fertilizer's material phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound usefulness.
Embodiment 3:a.Get 1000 liters of waste industrial phosphorizing liquids, through the chemical examination iron-holder is the 20g/ liter, adds the 1ml hydrogen peroxide by every gram iron/every liter and calculates, and then should add concentration and be 30% hydrogen peroxide 20000ml in 1000 liters of useless phosphatization liquid, be 30% ammoniacal liquor adding concentration then, stir while adding, measure pH value simultaneously, when pH value is 3, just stop to add ammoniacal liquor, iron precipitation in the at this moment useless phosphatization liquid is filtered, is separated, and removes the iron ion in the phosphatization liquid that gives up.
b。With sodium hydroxide, ammonium hydroxide, Wa-3 flocculation agent be by weight 25%, 8%, 4% all the other for the ratio of water is mixed with useless phosphatization liquid treatment agent, join with the useless phosphatization liquid treatment agent of 300Kg earlier and remove in the useless phosphatization liquid of de-iron, fully stir, add useless phosphatization liquid treatment agent more gradually, measure pH value simultaneously, the adjustment pH value is 8-9, at this moment, heavy metal in the useless phosphatization liquid all precipitates, and leaves standstill more than 4 hours, filters throw out is separated.
c。In the solution of elimination heavy metal, add 20Kg concentration again and be 30% ammoniacal liquor as changing agent, for fast reaction speed, can to add concentration again be 2% Fx-3 promotor, fully stir, utilize constant-temperature evaporation, separate obtaining phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound with quarternary phase diagram.
d。At last, the throw out that filtration is obtained is handled.In throw out, add nitric acid and make the throw out dissolving, adding potassium hydroxide then makes it form precipitation, add excessive potassium hydroxide heating again, making the resolution of precipitate of zinc change into zincate is dissolved in the solution, nickel still exists in solution with precipitated form, precipitate after filtration, washing, drying and dewatering, can be made into NiO.Add nitric acid again in filtrate, adjusting pH value is 8.5, and zincate changed into Zn (OH) and was precipitated out again this moment, after filtration, washing, drying and dewatering obtain white ZnO.Gained filtrate can be done with the filtrate merging of b step gained and be extracted composite fertilizer's material phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound usefulness.
Handle waste industrial phosphorizing liquid with the inventive method, can get product is iron, nickel oxide, zinc oxide and composite fertilizer material phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound.
Use ordinary method, fetch and receive 100 kilograms in zinc oxide, 200 kilograms of phosphoric acid and 300 kilograms of synthetic primary zinc phosphates of water, fetch and receive zinc oxide and nitric acid nitric acid synthesis zinc, fetch and receive nickel oxide and nitric acid nitric acid synthesis nickel.Can be made into new phosphatization liquid with institute's synthetic primary zinc phosphate, zinc nitrate, nickelous nitrate and Mazhev salt, nitrocalcite, manganous nitrate, additive.
Mix flyash or bentonite and additive again with the phosphorus-potassium compound that is reclaimed, nitrogen-potassium compound, phosphorus-nitrogen compound, iron, can be made into composite fertilizer.
Claims (8)
1. the treatment process of a waste industrial phosphorizing liquid comprises the steps:
A. separate out the iron in the useless phosphatization liquid;
B. separate out the heavy metal in the useless phosphatization liquid;
C. in the useless phosphatization liquid of separating out heavy metal, add transforming agent, after stirring evaporation, separate phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound;
D. the heavy metal of being separated out with the b step is produced nickel oxide, zinc oxide.
2. the treatment process of waste industrial phosphorizing liquid according to claim 1, it is characterized in that: described a step is the iron-holder of the useless phosphatization liquid of chemical examination, press 1g iron/liter adding 1ml hydrogen peroxide according to result of laboratory test, in useless phosphatization liquid, add hydrogen peroxide, pH value with the useless phosphatization liquid of ammoniacal liquor adjustment is 2-3 again, make the iron precipitation, filter to isolate the iron ion in the useless phosphatization liquid.
3. the treatment process of waste industrial phosphorizing liquid according to claim 1 and 2, it is characterized in that: described b step is for to be mixed with treatment agent with alkali, ammonium hydroxide, flocculation agent and water; Weight proportion is alkali 20%-25%, ammonium hydroxide 6%-8%, flocculation agent 2%-4%, and other is a water; Add treatment agent 100-300Kg in the useless phosphatization liquid of every kilolitre, fully stir, the adjustment pH value is 8-9, makes the heavy metal ion precipitation, leaves standstill, filters.
4. the treatment process of waste industrial phosphorizing liquid according to claim 3, it is characterized in that: described alkali is potassium hydroxide or sodium hydroxide.
5. the treatment process of waste industrial phosphorizing liquid according to claim 1, it is characterized in that: described c step is that the ammoniacal liquor of 20-30% is transforming agent for add concentration in the useless phosphatization liquid of separating out heavy metal, constant-temperature evaporation after fully stirring, with quarternary phase diagram separate phosphorus-potassium compound, nitrogen-potassium compound and phosphorus-nitrogen compound.
6. the treatment process of waste industrial phosphorizing liquid according to claim 5 is characterized in that: add conversion rate promotor again after adding transforming agent.
7. the treatment process of waste industrial phosphorizing liquid according to claim 1 is characterized in that: the heavy metal usefulness acid dissolving of described d step for the b step is separated out; Add alkali and make it to form precipitation, add alkali and heating again, filtering-depositing makes NiO through washing, drying and dewatering; Adding acid again in the filtrate, to adjust pH value be 8.5, produces new precipitation, after filtration, washing, drying and dewatering make ZnO.
8. the treatment process of waste industrial phosphorizing liquid according to claim 1, it is characterized in that: described acid is phosphoric acid or nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001229338A CN1153739C (en) | 2000-08-25 | 2000-08-25 | Process for treating waste industrial phosphorizing liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001229338A CN1153739C (en) | 2000-08-25 | 2000-08-25 | Process for treating waste industrial phosphorizing liquid |
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| CN1340466A true CN1340466A (en) | 2002-03-20 |
| CN1153739C CN1153739C (en) | 2004-06-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB001229338A Expired - Fee Related CN1153739C (en) | 2000-08-25 | 2000-08-25 | Process for treating waste industrial phosphorizing liquid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863099A (en) * | 2012-09-26 | 2013-01-09 | 深圳市柳溪机械设备有限公司 | Method and device for using phosphatized wastewater to produce pure water |
| CN102924148A (en) * | 2012-10-18 | 2013-02-13 | 大连碧城环保科技有限公司 | Process method for converting vegetable flower fertilizer by waste industrial phosphating solution |
| CN102965658A (en) * | 2012-10-19 | 2013-03-13 | 大连碧城环保科技有限公司 | Process technology for recycling discarded phosphating solution |
| CN102965660A (en) * | 2012-10-22 | 2013-03-13 | 大连碧城环保科技有限公司 | Method for quickly separating discarded phosphating solutions |
| WO2015003416A1 (en) * | 2013-07-12 | 2015-01-15 | Wang Endong | Environmentally friendly phosphoric acid concentrate used for dust removal, rust removal and phosphorization, and use thereof |
| CN105838383A (en) * | 2016-04-27 | 2016-08-10 | 上海立昌环境工程股份有限公司 | Treatment method for phosphated residues, soil restoration agent and method for reducing content of cadmium in rice |
-
2000
- 2000-08-25 CN CNB001229338A patent/CN1153739C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863099A (en) * | 2012-09-26 | 2013-01-09 | 深圳市柳溪机械设备有限公司 | Method and device for using phosphatized wastewater to produce pure water |
| CN102863099B (en) * | 2012-09-26 | 2014-04-16 | 深圳市柳溪机械设备有限公司 | Method and device for using phosphatized wastewater to produce pure water |
| CN102924148A (en) * | 2012-10-18 | 2013-02-13 | 大连碧城环保科技有限公司 | Process method for converting vegetable flower fertilizer by waste industrial phosphating solution |
| CN102965658A (en) * | 2012-10-19 | 2013-03-13 | 大连碧城环保科技有限公司 | Process technology for recycling discarded phosphating solution |
| CN102965660A (en) * | 2012-10-22 | 2013-03-13 | 大连碧城环保科技有限公司 | Method for quickly separating discarded phosphating solutions |
| WO2015003416A1 (en) * | 2013-07-12 | 2015-01-15 | Wang Endong | Environmentally friendly phosphoric acid concentrate used for dust removal, rust removal and phosphorization, and use thereof |
| CN105838383A (en) * | 2016-04-27 | 2016-08-10 | 上海立昌环境工程股份有限公司 | Treatment method for phosphated residues, soil restoration agent and method for reducing content of cadmium in rice |
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| Publication number | Publication date |
|---|---|
| CN1153739C (en) | 2004-06-16 |
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