CN107098445A - It is a kind of to utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater - Google Patents
It is a kind of to utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater Download PDFInfo
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- CN107098445A CN107098445A CN201710279943.6A CN201710279943A CN107098445A CN 107098445 A CN107098445 A CN 107098445A CN 201710279943 A CN201710279943 A CN 201710279943A CN 107098445 A CN107098445 A CN 107098445A
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- seawater
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- magnesium
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- 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
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
It is a kind of to utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater, belong to water pollution control and resource regeneration field, it includes following process：（1）Suspension and colloidality particulate matter in seawater is removed using pre-treating method, then separation of solid and liquid, the selective electrodialysis system that supernatant is pumped into setting carries out Mg2+Separation and concentration；（2）By step（1）Pole liquid obtained by middle selective electrodialysis system, which is added, carries out ammoniomagnesium phosphate crystal precipitation reaction in Nitrogen-and Phosphorus-containing waste water, control the pH stable of reaction 8.0 11.0 until reaction terminates by adding alkali；Separation of solid and liquid, reclaims the ammonium magnesium phosphate product that obtained sediment is recovery again.It is provided by the present invention it is a kind of separate using selective electrodialysis from seawater, the method for enriched magnesium, reclaimed for waste water ammonium magnesium phosphate and magnesium salts be provided, effectively reduce waste water recovery of nitrogen and phosphorus cost, reach the purpose that promotion waste water nitrogen phosphor resource is recycled.
Description
Technical field
The invention belongs to water pollution control and resource regeneration field, and in particular to one kind is separated using electrodialysis from seawater
Enriched magnesium, and magnesium salts is used for the method that waste water ammonium magnesium phosphate is reclaimed.
Background technology
The nitrogen phosphorus largely existed in waste water is the one of the main reasons of body eutrophication, and quality of water environment is caused seriously
Negative effect, it has also become current great environmental problem.The minimizing technology of nitrogen phosphorus mainly includes bioanalysis and physics in waste water
The major class of chemical method two.Bioanalysis has operating cost low, the features such as operational administrative is easy, but bioanalysis is low more suitable for handling
The nitrogen phosphorus waste water of concentration, and the nitrogen phosphorus waste water of physico-chemical process processing high concentration is more advantageous.Another aspect phosphorus is all
The indispensable nutrient of life form, is also the limited of phosphorus ore resource in important industrial chemicals, particularly nature
Property so that realize that recycling for phosphor resource is very necessary.Ammonium magnesium phosphate（MgNH4PO4·6H2O, is commonly called as guanite）The precipitation method
It is by Mg2+It is added in the sewage containing phosphate and ammonia nitrogen, the magnesium ammonium phosphate sediment of reaction generation indissoluble.Magnesium ammonium phosphate sediment
Method not only can remove and reclaim simultaneously nitrogen phosphorus to reduce the nitrogen and phosphorus load in waste water, and the ammonium magnesium phosphate being recovered to is one
Efficient slow-release fertilizer is planted, can agriculturally reused.
At present, the bottleneck of restriction ammonium phosphate magnesium processes commercial application is high for the process operation cost, and a key factor exists
In the selection of magnesium salts precipitating reagent.Currently widely used magnesium salts precipitating reagent is MgCl2, also have using Mg (OH) 2, magnesite, MgO
It is used as magnesium source.But these precipitating reagents limit the popularization and application of magnesium ammonium phosphate sediment method due to price factor.In seawater extensively
There is magnesium, be a kind of important potential magnesium source of waste water ammonium magnesium phosphate recovery process.However, the concentration of magnesium is relatively low in seawater, directly
Seawater is added to the concentration of nitrogen and phosphorus not only diluted in the reaction of waste water magnesium ammonium phosphate sediment in waste water, ammonium magnesium phosphate recovery is added
Difficulty；And tailwater quantity has been significantly greatly increased, cause follow-up tail water processing cost.Therefore, economic, feasible seawater point is researched and developed
From the method for, concentration magnesium salts, waste water ammonium magnesium phosphate cost recovery can be greatly reduced, environment and economic sustainable development is realized.
The content of the invention
The invention provides it is a kind of separated using selective electrodialysis from seawater, the method for enriched magnesium, be waste water phosphoric acid
Ammonium magnesium, which is reclaimed, provides magnesium salts, reduces waste water recovery of nitrogen and phosphorus cost, reaches the purpose that nitrogen phosphor resource is recycled in waste water.The present invention
It is characterised by that methods described step is：
（1）Suspension and colloidality particulate matter in seawater is removed using pre-treating method, then separation of solid and liquid, by supernatant liquid pump
The selective electrodialysis system for entering setting carries out the separation and concentration of magnesium；
（2）By step（1）Pole liquid obtained by middle selective electrodialysis system is added to progress ammonium magnesium phosphate knot in Nitrogen-and Phosphorus-containing waste water
Brilliant precipitation reaction, is terminated by the pH stable for adding alkali control reaction in 8.0-11.0 until reacting；Separation of solid and liquid, is obtained again
Sediment be recovery ammonium magnesium phosphate product；
（3）Step（1）Described in the pre-treating method of suspension in seawater and colloidality particulate matter be following methods combination：It is mixed
Solidifying, precipitation, filtering and membrane filtration；
（4）Step（1）Described in selective electrodialysis system by both sides electrode chamber and be clipped between the electrode chamber of both sides
Chamber is constituted；The chamber includes one or more chamber units, and each chamber unit is by the pole liquid room, the dope room that are arranged in order
Constituted with feed liquid room, pole liquid room and dope room are with the selective exchange membrane of monovalent cation（MVK）For interval, dope room and feed liquid room
With anion-exchange membrane（SA）For interval；If multiple chamber units, then feed liquid room and the pole liquid room of next chamber unit with
Cation-exchange membrane（SK）For interval；Handed between the chamber unit adjacent with the electrode chamber of both sides and electrode chamber with monopole cation
It is interval to change film（PC-SC）；The electrode chamber adjacent with feed liquid room is cathode chamber, and the electrode chamber adjacent with pole liquid room is anode chamber,
The positive plate being connected with the positive pole of dc source is provided with anode chamber, cathode chamber is provided with to be connected with the negative pole of dc source
The minus plate connect；MVK films when mounted cation exchange layer towards anode chamber；
（5）Step（1）Described in selective electrodialysis system operation method it is as follows：By sea water circulating pump selectable electrodialysis
The feed liquid room of system, concentration is not less than the pole of 0.05 mol/L strong electrolytic solution circulating pump selectable electrodialysis system
Liquid room, concentration is not less than the dope room of 0.05 mol/L strong electrolytic solution circulating pump selectable electrodialysis system, will
Concentration is not less than the electrode chamber of 0.05 mol/L electrode clean solution circulation pump selectable electrodialysis system；Pass through direct current
Source applies direct current to selective electrodialysis system and carries out selective electrodialysis, and in feed liquid room, electrical conductivity is not less than in 5 ms/cm
In the case of complete seawater in magnesium separation and concentration；
（6）Step（5）Described in selective electrodialysis system feed liquid room in be seawater；The selective electrodialysis system pole liquid
Strong electrolytic solution in room and dope room is sodium chloride, potassium chloride, sodium sulphate or potassium sulfate solution；The selective electrodialysis
Electrode clean solution is sulfamic acid sodium or metabisulfite solution in system electrode room；
（7）Step（5）Described in selective electrodialysis system operation current density be 10-100 mA/cm2。
Method proposed by the present invention by pre-processing the impurity of the suspension or colloidality that remove seawater, is then passed through first
Selective electrodialysis separation and concentration Mg2+, obtain high concentration contains Mg2+Concentrated water（1-10 g/L）Returned for waste water ammonium magnesium phosphate
Receive, waste water recovery of nitrogen and phosphorus cost can be greatly reduced, help to promote the disposal of resources of Nitrogen-and Phosphorus-containing waste water to utilize.
Brief description of the drawings
Fig. 1 selectivity electrodialysis membrane stack schematic diagrames.
Embodiment
The embodiments described below are only a part of embodiment of the invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
Embodiment 1：
The mg/L of suspended solid SS 12, colloidality particulate matter 6 mg/L, Mg in certain seawater2+ 800 mg/L、Na+ 10 g/L、
Cl- 12 g/L and SO4 2- 2000 mg/L.Certain livestock breeding wastewater, initial pH value 7.5, NH4 +And PO4 3-Concentration is respectively 1080
Mg/L and 96 mg/L.Pre-treatment is carried out to seawater using NF membrane.Supernatant after nanofiltration is pumped into the selective electric osmose of setting
Analysis system carries out Mg2+Separation and concentration, obtained in selective electrodialysis system contain Mg2+ 5g/L pole liquid；Then by pole liquid
Add livestock breeding wastewater and carry out ammoniomagnesium phosphate crystal reaction, add NaOH control ph stable in 9.0-9.5；Reaction terminates
Afterwards, the .5% of ammonium magnesium phosphate content 99 in the sediment reclaimed after testing.
The selective electrodialysis system set in above-mentioned steps by both sides electrode chamber and be clipped between the electrode chamber of both sides
Chamber constitute, each pair film size used is 80 × 80 mm；The chamber includes 5 chamber units, each chamber unit by
Pole liquid room, dope room and the feed liquid room being arranged in order are constituted, and pole liquid room and dope room are with the selective exchange membrane of monovalent cation
（MVK）For interval, dope room and feed liquid room are with anion-exchange membrane（SA）For interval；Feed liquid room and the pole of next chamber unit
Liquid room is with cation-exchange membrane（SK）For interval；With monopole sun between the chamber unit adjacent with the electrode chamber of both sides and electrode chamber
Amberplex is interval（PC-SC）；The electrode chamber adjacent with feed liquid room is cathode chamber, and the electrode chamber adjacent with pole liquid room is sun
The positive plate being connected with the positive pole of dc source is provided with pole room, anode chamber, cathode chamber is provided with negative with dc source
The minus plate that pole is connected；MVK films when mounted cation exchange layer towards anode chamber.
The method of operation of selective electrodialysis system is as follows in above-mentioned steps：By sea water circulating pump selectable electrodialysis system
The feed liquid room of system, by the pole liquid room of 0.5 mol/L sodium chloride solution circulating pump selectable electrodialysis system, by 0.5 mol/
The dope room of L sodium chloride solution circulating pump selectable electrodialysis system, by 1 mol/L sulfamic acid sodium solution circulating pump
The electrode chamber of selectable electrodialysis system；Direct current is applied to selective electrodialysis system by dc source and carries out selectivity
Electrodialysis, control electric current density is 30 mA/cm2；When feed liquid room electrical conductivity be 6 ms/cm when complete seawater in magnesium separation and
Concentration.
Claims (5)
1. a kind of utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater, its feature exists
It is in methods described step：
（1）Suspension and colloidality particulate matter in seawater is removed using pre-treating method, then separation of solid and liquid, by supernatant liquid pump
The selective electrodialysis system for entering setting carries out Mg2+Separation and concentration；
（2）By step（1）Pole liquid obtained by middle selective electrodialysis system, which is added in Nitrogen-and Phosphorus-containing waste water, carries out ammoniomagnesium phosphate crystal
Precipitation reaction, is terminated by the pH stable for adding alkali control reaction in 8.0-11.0 until reacting；Separation of solid and liquid, is obtained again
Sediment is the ammonium magnesium phosphate product of recovery.
2. one kind according to claim 1 utilizes selective electrodialysis separating magnesium and for waste water ammonium magnesium phosphate from seawater
The method of recovery, it is characterised in that described seawater pre-treating method is following methods combination：Coagulation, precipitation, filtering and membrane filtration.
3. one kind according to claim 1 utilizes selective electrodialysis separating magnesium and for waste water ammonium magnesium phosphate from seawater
The method of recovery, it is characterised in that described selective electrodialysis system by both sides electrode chamber and be clipped between the electrode chamber of both sides
Chamber constitute；The chamber include one or more chamber units, each chamber unit by be arranged in order pole liquid room, dope
Room and feed liquid room are constituted, and pole liquid room and dope room are with the selective exchange membrane of monovalent cation（MVK）For interval, dope room and feed liquid
Room is with anion-exchange membrane（SA）For interval；If multiple chamber units, then feed liquid room and the pole liquid room of next chamber unit
With cation-exchange membrane（SK）For interval；With monopole cation between the chamber unit adjacent with the electrode chamber of both sides and electrode chamber
Exchange membrane is interval（PC-SC）；The electrode chamber adjacent with feed liquid room is cathode chamber, and the electrode chamber adjacent with pole liquid room is anode
The positive plate being connected with the positive pole of dc source is provided with room, anode chamber, cathode chamber is provided with the negative pole with dc source
The minus plate being connected；MVK films when mounted cation exchange layer towards anode chamber.
4. one kind according to claim 1 utilizes selective electrodialysis separating magnesium and for waste water ammonium magnesium phosphate from seawater
The method of recovery, it is characterised in that described selective electrodialysis system operation method is as follows：By sea water circulating pump selectable
The feed liquid room of electrodialysis system, concentration is not less than 0.05 mol/L strong electrolytic solution circulating pump selectable electrodialysis system
The pole liquid room of system, concentration is not less than the dope of 0.05 mol/L strong electrolytic solution circulating pump selectable electrodialysis system
Room, concentration is not less than the electrode chamber of 0.05 mol/L electrode clean solution circulation pump selectable electrodialysis system；Pass through
Dc source applies direct current to selective electrodialysis system and carries out selective electrodialysis, and control electric current density is 10-100 mA/
cm2, the separation and concentration that magnesium in seawater is completed in the case of 5 ms/cm are not less than in feed liquid room electrical conductivity.
5. selective electrodialysis system according to claim 4, it is characterised in that be seawater in feed liquid room, pole liquid room and dense
Strong electrolytic solution in liquid room is that electrode clean solution is in sodium chloride, potassium chloride, sodium sulphate or potassium sulfate solution, electrode chamber
Sulfamic acid sodium or sodium sulphate.
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| CN201710279943.6A CN107098445B (en) | 2017-04-26 | 2017-04-26 | Method for separating magnesium from seawater and recycling magnesium ammonium phosphate in wastewater by using selective electrodialysis |
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| CN201710279943.6A CN107098445B (en) | 2017-04-26 | 2017-04-26 | Method for separating magnesium from seawater and recycling magnesium ammonium phosphate in wastewater by using selective electrodialysis |
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Cited By (4)
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| CN108325498A (en) * | 2018-01-05 | 2018-07-27 | 北京工业大学 | A method of synchronizing nitrogen phosphorus in recycling waste water using magnesium hydroxide modified meerschaum |
| CN108892117A (en) * | 2018-07-13 | 2018-11-27 | 中国科学技术大学 | A kind of guanite nano wire and preparation method thereof |
| CN110902898A (en) * | 2019-12-05 | 2020-03-24 | 浙江大学 | Device and method for removing nitrogen and phosphorus in sewage by magnesium anode electrodialysis method |
| WO2022222172A1 (en) * | 2021-04-19 | 2022-10-27 | 中国科学院城市环境研究所 | Continuous biogas slurry selective electrodialysis method, apparatus and system |
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Cited By (5)
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| WO2022222172A1 (en) * | 2021-04-19 | 2022-10-27 | 中国科学院城市环境研究所 | Continuous biogas slurry selective electrodialysis method, apparatus and system |
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