CN102616961A - Method for degrading organic pollutant and recycling phosphate in chemical nickel-plating waste liquid - Google Patents
Method for degrading organic pollutant and recycling phosphate in chemical nickel-plating waste liquid Download PDFInfo
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- CN102616961A CN102616961A CN2012100878657A CN201210087865A CN102616961A CN 102616961 A CN102616961 A CN 102616961A CN 2012100878657 A CN2012100878657 A CN 2012100878657A CN 201210087865 A CN201210087865 A CN 201210087865A CN 102616961 A CN102616961 A CN 102616961A
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Abstract
The invention discloses a method for degrading organic pollutant and recycling phosphate in chemical nickel-plating waste liquid, which belongs to the technical field of environment-friendly waste water treatment and resource recycle. The method conducts oxidation degradation of organic pollutant in waste water through the oxidation technology, simultaneously oxidizes hypophosphorous acid radical and phosphorous acid radical in waste water into orthophosphate radical and recycles phosphate and nickel by enabling the orthophosphate radical and nonmetal or metal ions to be precipitated. The method achieves resource recycle while treating waste water and has good environment benefits and economical benefits and wide application prospect.
Description
Technical field
The present invention discloses the phosphatic method of a kind of recovery; Being used for WWT and phosphor resource reclaims; Belong to and relate to that trade waste is handled and the technical field of resource utilization, organic pollutant and reclaim the method for orthophosphoric acid salt in particularly a kind of chemical nickel plating waste solution of degrading simultaneously.
Background technology
Chemical nickel plating is a kind of industrial surface treatment process of domestic and international widespread use; Chemical nickel plating has that coating is even, corrosion-resistant, hardness is high, wear resistance good, need not additional power source, the plating piece shape is not had advantages such as particular requirement; So obtained development rapidly; Chemical nickel plating is applied in the surface treatment process such as space flight, machinofacture, petrochemical complex, electronic industry, electric locomotive, plastics industry widely, is contemporary very important process for treating surface.But chemical nickel plating has also produced increasing environmental problem in widespread use.As reductive agent, single nickel salt is that the nickel process reaction formula of main salt is with inferior sodium phosphate:
NiSO
4+6NaH
2PO
2→Ni+2P?+2H
2+Na
2SO
4+4?NaH
2PO
3
Can find out that from reaction formula along with the carrying out of reaction process, because salinity and organic accumulation, the plating bath quality can descend, and causes plating bath to be scrapped at last.A large amount of pollution substances are contained in the chemical nickel plating waste solution the inside of scrapping, and mainly contain nickel ion, organism, Hypophosporous Acid, 50 root, orthophosphite, ortho-phosphoric acid root, sulfate radical, sodium ion etc.Wherein, nickel ion has 2 ~ 7g/L, is a kind of noble metal, and environmental pollution is serious, is carcinogenic substance, belongs to first kind pollutent; Total phosphorous have several grams whenever be raised to tens the gram every liter do not wait, phosphorus can cause body eutrophication, a large amount of phosphorus is discharged in the water severe water pollution; In addition, contain a large amount of organism in the aging liquid, more than the general 10000mg/L of COD, cause water pollution serious.
Treatment of Electroless Nickel Plating Wastewater mainly comprises three aspects: 1) organic degraded in the chemical nickel plating waste solution, and because of wherein organic concentration is very high, COD is mostly at several ten thousand milligrams every liter, and intractability is very big, does not have general effective ways at present; 2) from chemical nickle-plating wastewater, reclaim nickel, the technological comparative maturity of this direction, present most chemical nickle-plating wastewaters have all been realized the recovery of nickel; 3) phosphorus reclaims; The recovery technology of phosphorus also lags far behind, and its major cause is that phosphorus mainly exists with the form of inferior phosphorus with time phosphorus in the waste liquid; Can't be through directly precipitating with its effective removal; And ortho phosphorous acid root and orthophosphite are the material that is difficult to oxidation, and the general physical chemical process can't be with its oxidation, so recovery difficult is also very big.
To sum up, though contain a large amount of recyclable resources in the chemical nickle-plating wastewater, because there are a lot of technological insoluble problems, or make its treatment and purification difficulty big, resource reclaims difficulty.
Summary of the invention
To the above-mentioned prior art bottleneck of mentioning; Cause chemical nickle-plating wastewater seriously polluted, resource reclaims the problem of difficulty, and the present invention provides a kind of method of handling and fully utilizing chemical nickel plating waste solution; Chemical nickel plating waste solution is handled the time up to standard, therefrom reclaimed phosphoric acid salt.
In order to realize above purpose, technical scheme provided by the invention is: organic pollutant and reclaim phosphatic method in a kind of degraded chemical nickel plating waste solution, this method comprises the steps:
A, chemical nickel plating waste solution collected be discharged into equalizing tank;
B, the chemical nickel plating waste solution in the equalizing tank is filtered, remove particulate state suspended substance in the waste water;
C, nickel ion is reclaimed through IX, electrophoresis, method of replacement;
D, chemical nickel plating waste solution is carried out oxygenolysis handle, make wherein that the ortho phosphorous acid root is oxidized to the ortho-phosphoric acid root with orthophosphite, and make itself and nonmetal or metals ion formation calcium phosphate precipitation;
E, solid-liquid separation calcium phosphate precipitation and waste water, wastewater treatment COD, phosphorus, the back up to standard discharging of nickel content;
F, the phosphoric acid salt after will separating be dry, store.
Described chemical nickel plating waste solution does not use or used chemical nickel plating tank liquor for all.
Contain in nonmetallic ions such as organism, Hypophosporous Acid, 50 root, orthophosphite, ortho-phosphoric acid root, nickel ion and the metals ion one or more in the described chemical nickel plating waste solution.
Described oxidation technology comprises one or more the combination in common oxidation technology or ozone, CWO, ultraviolet catalytic wet oxidation, Fenton, type Fenton, the iron carbon bed.
Being used for phosphagenic nonmetallic ion and metals ion is that waste liquid itself contains, or adds in addition.
The kind that is used for phosphagenic nonmetallic ion and metals ion comprises the one or more combination of ammonium radical ion, mg ion, calcium ion, iron ion, aluminum ion.
The phosphatic method of dried recovered comprises one or more of spraying drying, lyophilize, oven drying, seasoning, microwave drying.
The invention has the beneficial effects as follows:
(1) provided by the inventionly from chemical nickel plating waste solution, reclaims phosphatic method,, can COD oxidative degradation in the chemical nickel plating waste solution be reached the environmental protection relevant emission standards because of it is an oxidation technology;
(2) in the organic while of oxidative degradation; Present technique can be oxidized to ortho phosphorous acid root and orthophosphite and be the ortho-phosphoric acid root; And add precipitation agent the ortho-phosphoric acid root is removed, thereby reach the purpose of removing phosphorus in the waste liquid, and make that phosphorus content is lower than the environmental protection relevant emission standards in the waste liquid;
(3) because organic oxidation removal has destroyed nickel ion and organic complex compound, make that the further removal of nickel ion is more thorough;
(4) because of having dropped into the precipitation agent of phosphate radical, can reclaim phosphoric acid salt, in disposing waste liquid, in COD and the phosphorus qualified discharge, realize the phosphor resource recovery, have very big environmental benefit and economic benefit.
To sum up, the method for the invention has that liquid waste disposal efficient is high, organism and phosphorus is removed thoroughly, clean process is green and reclaim plurality of advantages such as resource, has very high practical value, has a extensive future.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is further specified.
Description of drawings
Fig. 1 is a know-why schematic flow sheet of the present invention.
Embodiment
Present embodiment is the preferred embodiment for the present invention, and other all its principles are identical with present embodiment or proximate with substruction, all within protection domain of the present invention.
The embodiment of the invention provides in a kind of chemical nickel plating waste solution of degrading simultaneously organic pollutant and reclaims phosphatic method, comprises the steps:
A, chemical nickel plating waste solution collected be discharged into equalizing tank, described chemical nickel plating waste solution comprises that all do not use or used chemical nickel plating tank liquor; Wherein contain in nonmetallic ions such as organism, Hypophosporous Acid, 50 root, orthophosphite, ortho-phosphoric acid root, nickel ion and the metals ion one or more, and be not only limited to these ions; Can be that nickel ion was recovered, also can be not reclaim nickel;
B, the chemical nickel plating waste solution in the equalizing tank is filtered, remove particulate state suspended substance in the waste water;
C is if the waste liquid that has reclaimed through nickel can directly get into next step; If the waste liquid that does not reclaim through nickel can reclaim nickel ion earlier through IX, electrophoresis, method of replacement.
Chemical nickel plating waste solution is carried out oxygenolysis handle, make wherein that the ortho phosphorous acid root is oxidized to the ortho-phosphoric acid root with orthophosphite, and make itself and nonmetal or metals ion formation calcium phosphate precipitation; Described oxidation technology comprises various common oxidation technologies and various high-level oxidation technology, can be one or more the combination in common oxygenant oxidation or ozone, CWO, ultraviolet catalytic wet oxidation, Fenton, type Fenton, the iron carbon bed.
Drop into precipitation agent and reclaim phosphoric acid salt.Being used for phosphagenic nonmetallic ion and metals ion is that waste liquid itself contains, or adds in addition; The kind of nonmetallic ion and metals ion comprises the one or more combination in ammonium radical ion, mg ion, calcium ion, iron ion, the aluminum ion.
D solid-liquid separation calcium phosphate precipitation and waste water, wastewater treatment COD, phosphorus, the back up to standard discharging of nickel content.
Phosphoric acid salt after E will separate is through one or more the combination in the spraying drying, lyophilize, oven drying, seasoning, microwave drying etc.
Dry, the storage of phosphoric acid salt after F will separate; Dry intact phosphoric acid salt can be used for agricultural or industrial production.
To further specify the present invention with several specific exampless below:
Instance one:
Get 4 liters of chemical nickel plating waste solutions of having removed nickel ion, contain COD 20800mg/L, total phosphorus is 18g/L, and it is filtered back adding concentration is that 30% hydrogen peroxide (makes H
2O
2Concentration is 55g/L), adopt the mechanical stirring mode to stir, open 80W ultra violet lamp solution, start oxidizing reaction, react and close uv lamp after 2.5 hours.In the solution that has reacted, add 200g Al
2(SO
4)
3Continue to stir 30min, through filtering tertiary iron phosphate and water sepn, 105 ℃ of dryings of the tertiary iron phosphate after the separation 3 hours obtain the exsiccant tertiary iron phosphate at last.Last water outlet COD is 356mg/L, obtains exsiccant AlPO
4Be total to 71g.
Instance two:
Get 4 liters of chemical nickel plating waste solutions of having removed nickel ion, contain COD 26000mg/L, total phosphorus is 12g/L, and it is filtered back adding concentration is that 30% hydrogen peroxide (makes H
2O
2Concentration is 50g/L), adopt the mechanical stirring mode to stir, open 80W ultra violet lamp solution, start oxidizing reaction, react and close uv lamp after 3 hours.In the solution that has reacted, add 320g Fe
2(SO
4)
3Continue to stir 30min, through filtering tertiary iron phosphate and water sepn, 95 ℃ of dryings of the tertiary iron phosphate after the separation 5 hours obtain the exsiccant tertiary iron phosphate at last.Last water outlet COD is 451mg/L, obtains exsiccant FePO
42H
2O is 260g altogether.
Instance three:
Get 4 liters of chemical nickel plating waste solutions, contain nickel ion 6.125g/L, COD 26000mg/L, total phosphorus are 12g/L, and it is filtered back adding concentration is that 30% hydrogen peroxide (makes H
2O
2Concentration is 50g/L), add 445g FeSO simultaneously
47H
2O adopts the mechanical stirring mode to stir, and reacts 3 hours.After reaction finishes, by filtering ferric phosphate and moisture are left, 95 ℃ of dryings of the ferric phosphate after the separation 5 hours obtain dry ferric phosphate.Mother liquor spent ion exchange resin reclaim(ed) sulfuric acid nickel after the filtration, last water outlet COD is 451mg/L, obtains exsiccant FePO
42H
2O is 260g altogether.
Instance four:
Get 4 liters of chemical nickel plating waste solutions, contain COD 12000mg/L, H
2PO
2 -15.23g/L,, feed ozonation aerated (aeration speed 1 m in the reactor drum with putting into the uv ozone reactor drum after its filtration
3/ h, ozone concn 0.1mg/L), total coreaction 2 hours adds 188g Fe in the solution that has reacted
2(SO
4)
3Continue to stir 30min, through filtering tertiary iron phosphate and water sepn, 95 ℃ of dryings of the tertiary iron phosphate after the separation 5 hours obtain the exsiccant tertiary iron phosphate at last.Last water outlet COD is 482mg/L, obtains exsiccant FePO
42H
2O is 150g altogether
Instance five:
Get 4 liters of chemical nickel plating waste solutions, nickel ion is removed, and COD 26000mg/L, total phosphorus are 12g/L, and it is filtered back adding concentration is that 30% hydrogen peroxide (makes H
2O
2Concentration is 50g/L), add 445g FeSO simultaneously
47H
2O opens 80W ultra violet lamp solution, adopts the mechanical stirring mode to stir, and starts oxidizing reaction, reacts and closes uv lamp after 3 hours.After reaction finishes, by filtering ferric phosphate and moisture are left, 95 ℃ of dryings of the ferric phosphate after the separation 5 hours obtain dry ferric phosphate.Last water outlet COD is 221mg/L, obtains exsiccant FePO
42H
2O is 265g altogether.
Instance six:
Get 4 liters of chemical nickel plating waste solutions of having removed nickel ion, contain COD 12000mg/L, H
2PO
2 -15.23g/L it is filtered back adding concentration is that 30% hydrogen peroxide (makes H
2O
2Concentration is 20g/L), adopt the mechanical stirring mode to stir, open 80W ultra violet lamp solution, start oxidizing reaction, react and close uv lamp after 2 hours.In the solution that has reacted, add 188g Fe
2(SO
4)
3Continue to stir 30min, through filtering tertiary iron phosphate and water sepn, 95 ℃ of dryings of the tertiary iron phosphate after the separation 5 hours obtain the exsiccant tertiary iron phosphate at last.Last water outlet COD is 332mg/L, obtains exsiccant FePO
42H
2O is 152g altogether.
More than organic pollutant and reclaim phosphatic method and carried out detailed introduction in a kind of chemical nickel plating waste solution of degrading simultaneously that the embodiment of the invention is provided; For one of ordinary skill in the art; According to thought of the present invention, in implementation process, can be in embodiment and the range of application part that all changes; In sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. organic pollutant and reclaim phosphatic method in the degraded chemical nickel plating waste solution, this method comprises the steps:
A. chemical nickel plating waste solution is collected and be discharged into equalizing tank;
B. the chemical nickel plating waste solution in the equalizing tank is filtered, remove particulate state suspended substance in the waste water;
C. through IX, electrophoresis, method of replacement nickel ion is reclaimed;
D. chemical nickel plating waste solution is carried out oxygenolysis and handle, make wherein that the ortho phosphorous acid root is oxidized to the ortho-phosphoric acid root with orthophosphite, and make itself and nonmetal or metals ion formation calcium phosphate precipitation;
E. solid-liquid separation calcium phosphate precipitation and waste water, wastewater treatment COD, phosphorus, the back up to standard discharging of nickel content;
F. dry, the storage of the phosphoric acid salt after will separating.
2. organic pollutant and reclaim phosphatic method in the degraded chemical nickel plating waste solution according to claim 1 is characterized in that: described chemical nickel plating waste solution does not use or used chemical nickel plating tank liquor for all.
3. organic pollutant and reclaim phosphatic method in the degraded chemical nickel plating waste solution according to claim 1 is characterized in that: contain in nonmetallic ions such as organism, Hypophosporous Acid, 50 root, orthophosphite, ortho-phosphoric acid root, nickel ion and the metals ion one or more in the described chemical nickel plating waste solution.
4. according to organic pollutant in claim 1 or the 2 or 3 described degraded chemical nickel plating waste solutions and reclaim phosphatic method, it is characterized in that: described oxidation technology comprises one or more the combination in common oxidation technology or ozone, CWO, ultraviolet catalytic wet oxidation, Fenton, type Fenton, the iron carbon bed.
5. organic pollutant and reclaim phosphatic method in the degraded chemical nickel plating waste solution according to claim 1, it is characterized in that: being used for phosphagenic nonmetallic ion and metals ion is that waste liquid itself contains, or adds in addition.
6. according to organic pollutant in claim 1 or the 5 described degraded chemical nickel plating waste solutions and reclaim phosphatic method, it is characterized in that: the kind that is used for phosphagenic nonmetallic ion and metals ion comprises the one or more combination of ammonium radical ion, mg ion, calcium ion, iron ion, aluminum ion.
7. organic pollutant and reclaim phosphatic method in the degraded chemical nickel plating waste solution according to claim 1 is characterized in that: the phosphatic method of dried recovered comprises one or more of spraying drying, lyophilize, oven drying, seasoning, microwave drying.
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| CN102976531A (en) * | 2012-11-30 | 2013-03-20 | 冯云香 | Method for removing total phosphor by chemical nickel-plating wastewater treatment |
| CN103159364A (en) * | 2013-04-01 | 2013-06-19 | 埃梯星(厦门)电子科技有限公司 | Method for directly recovering phosphorus from chemical nickel-plating waste liquid |
| CN103224303A (en) * | 2013-04-11 | 2013-07-31 | 东莞道汇环保科技有限公司 | Chemical copper plating waste solution treatment method |
| WO2015106649A1 (en) * | 2014-01-15 | 2015-07-23 | 南京德磊科技有限公司 | Treatment method for electroless nickel plating solution |
| CN104876200A (en) * | 2015-04-21 | 2015-09-02 | 深圳市世清环保科技有限公司 | Method for recycling phosphorus resource from electroless nickel plating wastewater |
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| CN108275809A (en) * | 2018-01-31 | 2018-07-13 | 常州市武进天工机械制造有限公司 | Chemical nickel plating, electroplated zinc nickel alloy wastewater treatment method |
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| CN110395817A (en) * | 2019-07-25 | 2019-11-01 | 苏州湛清环保科技有限公司 | The recycling processing method of chemical nickel plating waste solution |
| CN110482513B (en) * | 2019-08-15 | 2021-06-29 | 广州科城环保科技有限公司 | Method for recovering granular ferric orthophosphate from chemical nickel plating waste liquid |
| CN110482513A (en) * | 2019-08-15 | 2019-11-22 | 广州科城环保科技有限公司 | A method of chemically nickel-plating waste liquid recycles graininess ferric orthophosphate |
| CN110668533A (en) * | 2019-11-02 | 2020-01-10 | 深圳市世清环保科技有限公司 | Method and system for treating alkaline chemical nickel plating wastewater |
| CN110759540A (en) * | 2019-11-25 | 2020-02-07 | 湖南中湘春天环保科技有限公司 | Treatment method of chemical nickel plating waste liquid |
| CN110759540B (en) * | 2019-11-25 | 2022-04-22 | 湖南中湘春天环保科技有限公司 | Treatment method of chemical nickel plating waste liquid |
| CN112158978A (en) * | 2020-09-14 | 2021-01-01 | 浙江海拓环境技术有限公司 | Method for treating hypophosphite in chemical nickel plating waste liquid |
| CN112158978B (en) * | 2020-09-14 | 2021-08-10 | 浙江海拓环境技术有限公司 | Method for treating hypophosphite in chemical nickel plating waste liquid |
| CN113060868A (en) * | 2021-03-30 | 2021-07-02 | 哈尔滨工业大学（深圳） | Treatment method and treatment system for chemical nickel plating wastewater |
| CN113636691A (en) * | 2021-07-23 | 2021-11-12 | 生态环境部华南环境科学研究所 | Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid |
| CN114605023A (en) * | 2022-02-22 | 2022-06-10 | 深圳市世清环保科技有限公司 | Treatment method of high-concentration phosphorus-containing wastewater of chemical nickel plating |
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