CN103011460A - Novel process for removing phosphorus from metal-salt-containing waste phosphoric acid - Google Patents
Novel process for removing phosphorus from metal-salt-containing waste phosphoric acid Download PDFInfo
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- CN103011460A CN103011460A CN201210576189XA CN201210576189A CN103011460A CN 103011460 A CN103011460 A CN 103011460A CN 201210576189X A CN201210576189X A CN 201210576189XA CN 201210576189 A CN201210576189 A CN 201210576189A CN 103011460 A CN103011460 A CN 103011460A
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Abstract
The invention relates to a novel process for removing phosphorus from metal-salt-containing waste phosphoric acid, comprising the following steps of: (1) neutralizing lime to obtain calcium phosphate sediment; (2) primarily filtering to filter out solid or colloidal particles in a waste solution; and (3) carrying out adsorption and phosphorus removal on residual phosphate radicals in the waste solution by utilizing chlorine type strong-basicity anion exchange resin, wherein effluent is a phosphorus-free solution which can be directly discharged or is subjected to conventional wastewater treatment, and a phosphorus-containing salt solution desorbed from an ion exchange resin bed can be returned to the last step to be circulated. According to the novel process disclosed by the invention, a chemical ion exchange method is used to replace a biological technology which is sensitive to an environment to treat the waste phosphoric acid, so that phosphorus in the waste phosphoric acid can be effectively removed, phosphorus content in wastewater reaches a national discharging standard and the treatment effect is very stable; and the by-product calcium phosphate can also be used as a phosphate fertilizer to be recycled.
Description
Technical field
The present invention relates to a kind of technical field of waste water processing, be specifically related to a kind of Dephosphorization New Technique of metal-containing salt waste phosphoric acid.
Background technology
At present, some chemical industry in the metal finishing processing procedures such as aluminium electrolutic capacitor aluminium foil, iron and steel, can produce a large amount of waste phosphoric acids.The traditional method of processing these waste phosphoric acids is direct discharging a bit, serious environment pollution; Some is to neutralize with lime; not only increase processing cost but also can produce a large amount of mud, solution still contains a small amount of phosphonium ion, and China's emission standard of phosphorus that has been the water conservation strict supervision in recent years; this method with the lime neutralization, the discharging of phosphorus can not reach new environmental protection standard.The way that also has is to use bioremediation, but that this also has is multiple undesirable.Therefore, the waste phosphoric acid treatment process of a kind of emission standard that can reach phosphorus of research and development is to become technical problem in the urgent need to address.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of Dephosphorization New Technique of metal-containing salt waste phosphoric acid is provided, can making after treatment, the discharging of phosphorus reaches environmental protection standard.
Purpose of the present invention is achieved through the following technical solutions:
A kind of Dephosphorization New Technique of metal-containing salt waste phosphoric acid comprises the steps:
(1), lime neutralization and preliminary filtration the: in metal-containing salt waste phosphoric acid solution, add lime, reaction generates the calcium phosphate precipitation that is slightly soluble in water, then filter, described filtration unit comprises that the plate-and-frame filter press filter residue of serial or parallel connection setting is calcium phosphate and metal hydroxides mixed precipitation, and filtrate being contains the sewage solution of micro-calcium phosphate;
(2), the smart filtration: the filtrate that step (1) is obtained is sent into fine filtering apparatus and is carried out essence and filter, and consolidates on a small quantity type or colloidal particle in the filtering filtrate; Described filtration unit comprises back-flushing filter and cartridge filter;
(3), ion exchange resin dephosphorization: will send into again in the ion exchange resin dephosphorization system through the filtrate that obtains after the smart filtration of step (2) and process; Described ion exchange resin dephosphorization system comprise can the Phosphate Sorption acid ion chlorine-based strong alkali anionite-exchange resin; The filtrate that obtains after the smart filtration of step (2) at first passes in the described chlorine-based strong alkali anion exchange resin bed, phosphate anion is adsorbed, the effluent liquid that from described chlorine-based strong alkali anion exchange resin bed, flows out be the chloride containing calcium salt without phosphorus solution, it is disposed in the conventional Waste Water Treatment; In described chlorine-based strong alkali anion exchange resin bed, pass into the phosphate radical that adsorbs in this resin bed of sodium chloride aqueous solution desorption again, desorption effluent liquid out is back to step (1) and processes, and repeats above-mentioned (1), (2), (3) step.
Further, the Dephosphorization New Technique of above-mentioned metal-containing salt waste phosphoric acid, in the step (2), the pore size filter of described back-flushing filter is between 1～100 μ m.
Further, the Dephosphorization New Technique of above-mentioned metal-containing salt waste phosphoric acid, in the step (2), described cartridge filter adopts disposable polypropylene filter core.
The substantive distinguishing features that technical solution of the present invention is outstanding and the progress that is showing are mainly reflected in:
The Dephosphorization New Technique of metal-containing salt waste phosphoric acid of the present invention, utilize the chemical ion exchange process to replace the biotechnology of environment sensitive is processed waste phosphoric acid, can effectively remove the phosphorus in the phosphate discharge liquid, make the phosphorus content in the waste water reach discharging standards, result is very stable, and by product calcium phosphate of the present invention also can be used as the phosphate fertilizer recycling.
Description of drawings
Below in conjunction with accompanying drawing technical solution of the present invention is described further:
Fig. 1 utilizes Technology of the present invention to process the treating processes synoptic diagram that contains the aluminium waste phosphoric acid;
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail.
Embodiment
Present embodiment take phosphoric acid quality concentration be about 1%, the aluminum ion mass concentration contains the aluminium waste phosphoric acid as pending waste liquid as 4500ppm's, utilizes technique of the present invention that this waste liquid is carried out dephosphorization and processes, referring to Fig. 1, detailed process is as follows:
(1), lime neutralization and preliminary the filtration: add lime to containing in the aluminium waste phosphoric acid solution, reaction generates the calcium phosphate precipitation that is slightly soluble in water, then filters, and filter residue is the mixed precipitation of calcium phosphate and aluminium hydroxide, and filtrate being contains the sewage solution of micro-calcium phosphate.Filter residue can be used as phosphate fertilizer and recycles, and filtrate is then sent into the lower step and processed.
(2), the smart filtration: the filtrate that step (1) is obtained is sent into filtration unit and is carried out essence and filter, and mainly solid type or the colloidal particle in the filtering waste phosphoric acid prefiltration gained waste liquid avoid stopping up the follow-up equipment such as ion exchange resin; This goes on foot back-flushing filter and cartridge filter that employed filtration unit comprises that serial or parallel connection arranges, and the pore size filter of described back-flushing filter is between 1-100 μ m, and what described cartridge filter adopted is disposable polypropylene (PP) filter core.Through filtering phosphate radical (PO in the filtrate that obtains
4 3+) content is about 20ppm.
(3), the ion exchange resin dephosphorization: will send into again in the ion exchange resin dephosphorization system through the filtrate that step (2) is preliminary to be obtained after filtering and process, this ion exchange resin dephosphorization system comprise can the Phosphate Sorption acid ion chlorine-based strong alkali anionite-exchange resin.At first will pass in the described chlorine-based strong alkali anion exchange resin bed through the filtrate that step (2) is preliminary to be obtained after filtering, phosphate anion is attracted in the resin bed, effluent liquid be the chloride containing calcium salt without phosphorus solution (PO
4 3+＜1ppm), it can directly discharge or carry out further wastewater treatment; Pass into mass concentration in the described chlorine-based strong alkali anion exchange resin bed again and be the phosphate radical that adsorbs in sodium chloride aqueous solution (being the NaCl regenerated liquid) this resin bed of desorption of about 10%, desorption effluent liquid out (mainly is Na
3PO
4) be back to again step (1) and carry out calcium phosphate precipitation and process, and repeat to loop above-mentioned (1), (2), (3) step, until till the residual phosphorus acid group removes fully.
It is simple and easy to do that present embodiment contains the treating processes of aluminium phosphate discharge liquid, and result is very stable.After treatment, not only making the content of phosphorus reach emission standard, can also obtain by product phosphate fertilizer, is very economical and practical a kind of Dephosphorization New Technique therefore, is worthy of popularization.
What need to understand is: above-mentioned explanation is not to be limitation of the present invention, and in the present invention conceived scope, the interpolation of carrying out, conversion, replacement etc. also should belong to protection scope of the present invention.
Claims (3)
1. the Dephosphorization New Technique of a metal-containing salt waste phosphoric acid is characterized in that: comprise the steps:
(1), lime neutralization and preliminary filtration the: in metal-containing salt waste phosphoric acid solution, add lime, reaction generates the calcium phosphate precipitation that is slightly soluble in water, then filter, described filtration unit comprises that the plate-and-frame filter press filter residue of serial or parallel connection setting is calcium phosphate and metal hydroxides mixed precipitation, and filtrate being contains the sewage solution of micro-calcium phosphate;
(2), the smart filtration: the filtrate that step (1) is obtained is sent into fine filtering apparatus and is carried out essence and filter, and consolidates on a small quantity type or colloidal particle in the filtering filtrate; Described filtration unit comprises back-flushing filter and cartridge filter;
(3), ion exchange resin dephosphorization: will send into again in the ion exchange resin dephosphorization system through the filtrate that obtains after the smart filtration of step (2) and process; Described ion exchange resin dephosphorization system comprise can the Phosphate Sorption acid ion chlorine-based strong alkali anionite-exchange resin; The filtrate that obtains after the preliminary filtration of step (2) at first passes in the described chlorine-based strong alkali anion exchange resin bed, phosphate anion is adsorbed, the effluent liquid that from described chlorine-based strong alkali anion exchange resin bed, flows out be the chloride containing calcium salt without phosphorus solution, directly the discharging or further drain in the Waste Water Treatment; In described chlorine-based strong alkali anion exchange resin bed, pass into the phosphate radical that adsorbs in this resin bed of sodium chloride aqueous solution desorption again, desorption effluent liquid out is back to step (1) and processes, and repeats above-mentioned (1), (2), (3) step.
2. the Dephosphorization New Technique of metal-containing salt waste phosphoric acid according to claim 1, it is characterized in that: in the step (2), the pore size filter of described back-flushing filter is between 1～100 μ m.
3. the Dephosphorization New Technique of metal-containing salt waste phosphoric acid according to claim 1, it is characterized in that: in the step (2), described cartridge filter adopts disposable polypropylene filter core.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210576189XA CN103011460A (en) | 2012-12-27 | 2012-12-27 | Novel process for removing phosphorus from metal-salt-containing waste phosphoric acid |
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| CN201210576189XA CN103011460A (en) | 2012-12-27 | 2012-12-27 | Novel process for removing phosphorus from metal-salt-containing waste phosphoric acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011991A (en) * | 2017-04-12 | 2017-08-04 | 西北大学 | A kind of resin cation dephosphorization method of grease |
| CN108993444A (en) * | 2018-08-01 | 2018-12-14 | 华中农业大学 | A kind of composite dephosphorization adsorbent and water body dephosphorized method |
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| CN101679038A (en) * | 2007-03-19 | 2010-03-24 | 易开采瑞典有限公司 | phosphorus recovery |
| CN102421703A (en) * | 2009-05-12 | 2012-04-18 | 索尔维公司 | Process for the recovery of phosphate values from a waste solution |
| CN102701489A (en) * | 2012-06-29 | 2012-10-03 | 上海大学 | Three-step process for high-concentration phosphorus-containing wastewater by calcium aluminum compound |
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Patent Citations (4)
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| US20080053909A1 (en) * | 2006-09-06 | 2008-03-06 | Fassbender Alexander G | Ammonia recovery process |
| CN101679038A (en) * | 2007-03-19 | 2010-03-24 | 易开采瑞典有限公司 | phosphorus recovery |
| CN102421703A (en) * | 2009-05-12 | 2012-04-18 | 索尔维公司 | Process for the recovery of phosphate values from a waste solution |
| CN102701489A (en) * | 2012-06-29 | 2012-10-03 | 上海大学 | Three-step process for high-concentration phosphorus-containing wastewater by calcium aluminum compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011991A (en) * | 2017-04-12 | 2017-08-04 | 西北大学 | A kind of resin cation dephosphorization method of grease |
| CN107011991B (en) * | 2017-04-12 | 2021-04-13 | 西北大学 | Cationic resin dephosphorization method for grease |
| CN108993444A (en) * | 2018-08-01 | 2018-12-14 | 华中农业大学 | A kind of composite dephosphorization adsorbent and water body dephosphorized method |
| CN108993444B (en) * | 2018-08-01 | 2021-07-30 | 华中农业大学 | Composite phosphorus removal adsorbent and water body phosphorus removal method |
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Application publication date: 20130403 |