CN104817154A - Method for recovering ammonia nitrogen in wastewater - Google Patents
Method for recovering ammonia nitrogen in wastewater Download PDFInfo
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- CN104817154A CN104817154A CN201510161103.0A CN201510161103A CN104817154A CN 104817154 A CN104817154 A CN 104817154A CN 201510161103 A CN201510161103 A CN 201510161103A CN 104817154 A CN104817154 A CN 104817154A
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- ammonium phosphate
- magnesium ammonium
- waste water
- ammonia nitrogen
- ammonia
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- 239000002351 wastewater Substances 0.000 title claims abstract description 72
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 53
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims abstract description 112
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 110
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 64
- 238000004064 recycling Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 54
- 238000000909 electrodialysis Methods 0.000 abstract description 13
- 150000001450 anions Chemical class 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 description 15
- 238000011084 recovery Methods 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- -1 phosphate anion Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 239000002894 chemical waste Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical class [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- JGXQUVHKSJKROR-UHFFFAOYSA-N [N].N.N Chemical compound [N].N.N JGXQUVHKSJKROR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GISGYEHPOAIOTM-UHFFFAOYSA-L [O-]P([O-])(O)=O.OP(O)(O)=O.N.N.N.[Mg+2] Chemical compound [O-]P([O-])(O)=O.OP(O)(O)=O.N.N.N.[Mg+2] GISGYEHPOAIOTM-UHFFFAOYSA-L 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The present invention discloses a method for recovering ammonia nitrogen in wastewater, and belongs to the field of wastewater treatment. The steps comprise: dissolving the recovered magnesium ammonium phosphate solid in an acid solution to obtain a magnesium ammonium phosphate solution with a certain mass fraction; injecting the obtained magnesium ammonium phosphate solution into the separation pole chambers of an electrodialysis system to carry out anion and cation separation, and treating according to a certain operating parameters; after completing the treating, pouring the products of the anode chamber and the cation chamber to wastewater according to a certain ratio to obtain magnesium ammonium phosphate crystal precipitate so as to achieve the purpose of removal of ammonia from the wastewater; and recovering the magnesium ammonium phosphate crystal, dissolving in an acid solution to prepare the magnesium ammonium phosphate solution with a certain mass fraction, injecting into the pole chambers to carry out the separation treatment, and pouring the products of the anode chamber and the cation chamber to the wastewater to circularly remove the ammonia after completing the treating. With the method of the present invention, the problem of the high agent cost of the magnesium ammonium phosphate method can be effectively solved, and the difficult problem that the ammonia nitrogen removal rate is reduced along with the increase of the number of the magnesium ammonium phosphate circulation ammonia removal is solved.
Description
Technical field
The present invention relates to a kind of method reclaiming ammonia nitrogen in waste water, more particularly, be a kind of ammonia nitrogen waste water circulation process method of economy, efficiently can remove the ammonia nitrogen in waste water, belong to field of waste water treatment.
Background technology
In recent years, ammoniomagnesium phosphate crystal sinks ammonia process and obtains and study widely.Ammoniomagnesium phosphate crystal method is formed magnesium ammonium phosphate crystal by the ammonia nitrogen added in ammonia nitrogen waste water in solubility magnesium salts and phosphoric acid salt and waste water and reached the object removing ammonia nitrogen.This method can solve the problem of the biochemical suppression wastewater biochemical denitrification effect differences such as coal chemical industrial waste water and magnesium ammonium phosphate is good slow-release fertilizer, and while removal ammonia nitrogen in waste water, precipitated product also can carry out recycling.But reagent cost is too high limits promoting the use of of ammonium phosphate magnesium processes, it is a difficult point of this method research.
For the difficult problem that reagent cost is too high, Chinese scholars proposes some terms of settlement.The article delivered mainly contains: this type of technology mainly reaches by the circulation of magnesium ammonium phosphate pyrolysis product the effect reducing reagent cost, ammonia rate is released in order to what improve magnesium ammonium phosphate pyrolysis, in magnesium ammonium phosphate pyrolytic process, add sodium hydroxide solution, improve the release of ammonia nitrogen in magnesium ammonium phosphate pyrolytic process.The research such as Tao Zhang shows, by pyrolysis magnesium ammonium phosphate ammonia nitrogen release rate more than 90%.But in magnesium ammonium phosphate pyrolytic process, pyrolysis product and excessive water vapor form phosphoric acid salt magnesium, and phosphoric acid salt magnesium is the same with magnesium ammonium phosphate, finally resolve into secondary magnesium phosphate, but phosphoric acid salt magnesium is more stable than magnesium ammonium phosphate performance, required pyrolysis temperature is higher, and pyrolysis time is longer.Therefore, in magnesium ammonium phosphate pyrolytic process, add sodium hydroxide solution, although the release rate of ammonia nitrogen can be improved, can energy consumption be improved simultaneously, increase cost for wastewater treatment.
When Shilong He etc. utilizes magnesium ammonium phosphate pyrolysis product circular treatment percolate, first time ammonia nitrogen removal frank reach 84%, then reduce to 62% the 6th time; When Mustafa Trker etc. utilizes magnesium ammonium phosphate pyrolysis product circular treatment anaerobic supernatant, first time ammonia nitrogen removal frank reach 92%, then reduce to 77% the 5th time.In the heavy ammonia process of magnesium ammonium phosphate circulation, along with the increase of cycle index, obviously declining appears in ammonia nitrogen removal frank.Shigeru Sugiyama etc. thinks, in magnesium ammonium phosphate pyrolytic process, is attended by the generation of magnesium pyrophosphate derivative, and the heavy ammonia poor ability of magnesium pyrophosphate.Along with the increase of cycle index, magnesium pyrophosphate content progressively rises, and causes ammonia nitrogen removal frank obviously to decline along with the increase of cycle index.So far, there is not yet a kind of running cost low, recovering effect stablized, the relevant report of efficient recycling method.
Summary of the invention
The problem that in waste water, ammonia nitrogen cost is high, recycling efficiency is not high is removed for ammoniomagnesium phosphate crystal method in prior art, the invention provides the method for ammonia nitrogen in a kind of recovery waste water of economy, it effectively can solve the too high problem of ammoniomagnesium phosphate crystal method reagent cost, solves pyrolysis simultaneously and reclaims in magnesium ammonium phosphate method along with the difficult problem that the increase ammonia nitrogen removal frank of the heavy ammonia number of times of magnesium ammonium phosphate circulation declines.
The method of ammonia nitrogen in recovery waste water of the present invention, specifically comprises the following steps:
(1) the magnesium ammonium phosphate crystal reclaimed in wastewater treatment is dropped into acidic solution and carry out acidolysis, acidolysis 1 ~ 3h at 10 DEG C ~ 60 DEG C temperature, be configured to the magnesium ammonium phosphate solution that massfraction is 5% ~ 70%, be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 10 ~ 40ma/cm
2condition under, be separated 2 ~ 5h, obtain the anolyte compartment after separation and cathode compartment product;
(2) in waste water, add anolyte compartment and cathode compartment product that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 0.9 ~ 1.4:1:0.6 ~ 1.3, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water;
(3) the magnesium ammonium phosphate crystalloid solution in recycling step (2) is in acid solution, and acidolysis 1 ~ 3h at 10 DEG C ~ 60 DEG C temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 5% ~ 70%; Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 10 ~ 40ma/cm
2condition under, be separated 2 ~ 5h, obtain the anolyte compartment after separation and cathode compartment product, drop into waste water circulation except ammonia.
In the present invention, magnesium ammonium phosphate crystal is a kind of caustic crystals, can be dissolved in acid solution, the magnesium ammonium phosphate dissolution of crystals reclaimed in wastewater treatment is configured in acid solution the magnesium ammonium phosphate solution of certain mass mark, now contain a large amount of magnesium ions in magnesium ammonium phosphate solution, phosphate anion and ammonium radical ion; Anion and cation exchange membrane has selective penetrated property, and anode membrane only allows positively charged ion to pass through, and cavity block only allows negatively charged ion to pass through, and utilizes ion-exchange membrane can realize the removal of being separated of phosphate radical and magnesium ion and ammonium radical ion simultaneously.Be injected into by magnesium ammonium phosphate solution in room, membrane sepn pole, regulate the current density of electrodialysis system, control disengaging time, after process, separated product is dropped into waste water ammonia-removal, recovery magnesium ammonium phosphate solid circulation sinks ammonia.
(1) the present invention adopts the product circulation of magnesium ammonium phosphate acid hydrolysis solution after electrodialysis system is separated except the technical scheme of ammonia, not only reduce ammoniomagnesium phosphate crystal method and sink the reagent cost of ammonia, and, reclaim while can realizing phosphate radical and magnesium ion, reclaiming in product process does not have by product to produce, and organic efficiency is high; In working cycle, do not exist along with magnesium ammonium phosphate acid hydrolysis solution through electrodialysis system be separated after product circulation except ammonia cycle index increase except ammonia rate decline problem.
(2) in the process that magnesium ammonium phosphate acid hydrolysis solution is separated through electrodialysis system, in step (1), the pH of acidic solution be less than 4 can, acidolysis temperature is room temperature, the acidolysis time is 1 ~ 2 h magnesium ammonium phosphate solution massfraction is 10% ~ 50%, separation current density is 25 ~ 35ma/cm
2, disengaging time is 2.5 ~ 3 h, the rate of recovery of phosphate radical and magnesium ion is divided can reach 93% ~ 100%, 80% ~ 90%; The rate of recovery of phosphate radical and magnesium ion be separated current density, being proportionate property of disengaging time, be reduce energy consumption, improve separation efficiency, obtain the brilliant ion rate of recovery of higher one-tenth simultaneously, known by experimental result, when separation current density is 30 ~ 35ma/cm
2, disengaging time is 3 h, becomes the brilliant ion rate of recovery to reach 98%.
(3) magnesium ammonium phosphate solution is in electrodialysis system sepn process, and seldom have by product to generate, this method utilizes the method for physical sepn, and the product of anode concentration compartments is mainly with phosphate solution, and negative electrode concentration compartments mainly produces magnesium hydrate precipitate; Whole system is easy for the transformation of existing Sewage treatment systems, electrodialysis system simple to operate, and controling parameters is few, is a kind of simple efficient method.
Accompanying drawing explanation
Fig. 1 removes coal gasification waste water ammonia nitrogen design sketch in embodiment 1;
Fig. 2 removes coking chemical waste water ammonia nitrogen design sketch in embodiment 2;
Fig. 3 removes vanadium waste ammonia nitrogen design sketch processed in embodiment 3;
Fig. 4 removes fertilizer industrial wastewater ammonia nitrogen design sketch in embodiment 4;
Fig. 5 removes breeding wastewater ammonia nitrogen design sketch in embodiment 5;
Fig. 6 removes synthetic ammonia ammonia nitrogen in waste water design sketch in embodiment 6.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1
The method of ammonia nitrogen in gas recovery waste water described in the present embodiment, specifically comprises the following steps:
(1) carry out acidolysis, acidolysis 3h at 10 DEG C of temperature by the magnesium ammonium phosphate crystal reclaimed in wastewater treatment input acid solution, be configured to the magnesium ammonium phosphate solution that massfraction is 20%; Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 20ma/cm
2condition under, be separated 3h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte compartment and cathode compartment product that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 1.4:1:0.6, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystal in recycling step (2), is put in acid solution and is carried out acidolysis, acidolysis 1h at 30 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 10%.Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 30ma/cm
2condition under, be separated 2h, obtain the anolyte compartment after separation and cathode compartment product, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove coal gasification waste water ammonia nitrogen effect and see Fig. 1; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 87%, and along with the increase of cycle index, heavy ammonia rate change is not obvious.
By method of the present invention, the medicament expense not only greatly reducing ammonium phosphate magnesium processes process high-concentration ammonia nitrogenous wastewater is used, and maintain a higher ammonia nitrogen removal effect, ammonia nitrogen in waste water content after process is at 83 mg/L, facilitate the subsequent disposal of waste water, precipitated product also resourcebility utilization simultaneously.
Embodiment 2
Reclaim the method for ammonia nitrogen in coking chemical waste water described in the present embodiment, specifically comprise the following steps:
(1) the magnesium ammonium phosphate crystal reclaimed in wastewater treatment is put in acid solution carry out acidolysis, acidolysis 1h at 60 DEG C of temperature, be configured to the magnesium ammonium phosphate solution that massfraction is 30%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 10ma/cm
2condition under, be separated 2h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte compartment and cathode compartment product that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 0.9:1:1.3, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystal in recycling step (2), is put in acid solution and is carried out acidolysis, acidolysis 3h at 10 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 70%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 10ma/cm
2condition under, be separated 3h, obtain the anolyte after separation and cathode deposition, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove coking chemical waste water ammonia nitrogen effect and see Fig. 2; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 85%, and along with the increase of cycle index, heavy ammonia rate change is not obvious.
Embodiment 3
In the recovery vanadium waste of a kind of economy of the present embodiment, the method for ammonia nitrogen, the steps include:
(1) by the magnesium ammonium phosphate dissolution of crystals that reclaims in wastewater treatment in acid solution, acidolysis 1h at 30 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 50%.Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 40ma/cm
2condition under, be separated 2h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte and cathode deposition that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 1.2:1:1.1, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystalloid solution in recycling step (2) is in acid solution, and acidolysis 1h at 60 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 5%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 40ma/cm
2condition under, be separated 5h, obtain the anolyte compartment after separation and cathode compartment product, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove vanadium waste ammonia nitrogen effect processed and see Fig. 3; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 97%, and along with the increase of cycle index, heavy ammonia rate change is not obvious.
Embodiment 4
In the recovery fertilizer industrial wastewater of a kind of economy of the present embodiment, the method for ammonia nitrogen, the steps include:
(1) by the magnesium ammonium phosphate dissolution of crystals that reclaims in wastewater treatment in acid solution, acidolysis 2h at 30 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 50%.Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 30ma/cm
2condition under, be separated 3h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte and cathode deposition that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 1.2:1.0:1.1, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystalloid solution in recycling step (2) is in acid solution, and acidolysis 2h at 40 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 5%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 35ma/cm
2condition under, be separated 5h, obtain the anolyte compartment after separation and cathode compartment product, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove fertilizer industrial wastewater ammonia nitrogen effect and see Fig. 4; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 95%, and along with the increase of cycle index, heavy ammonia rate change is not remarkable.
Embodiment 5
In the recovery breeding wastewater of a kind of economy of the present embodiment, the method for ammonia nitrogen, the steps include:
(1) by the magnesium ammonium phosphate dissolution of crystals that reclaims in wastewater treatment in acid solution, acidolysis 1.5h at 40 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 40%.Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 35ma/cm
2condition under, be separated 3h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte and cathode deposition that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 1.2:1:1.0, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystalloid solution in recycling step (2) is in acid solution, and acidolysis 1h at 35 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 30%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 25ma/cm
2condition under, be separated 3h, obtain the anolyte compartment after separation and cathode compartment product, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove breeding wastewater ammonia nitrogen effect and see Fig. 5; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 96%, and along with the increase of cycle index, heavy ammonia rate keeps stable.
Embodiment 6
In the recovery synthetic ammonia waste water of a kind of economy of the present embodiment, the method for ammonia nitrogen, the steps include:
(1) by the magnesium ammonium phosphate dissolution of crystals that reclaims in wastewater treatment in acid solution, acidolysis 2h at 30 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 20%.Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 40ma/cm
2condition under, be separated 2h, obtain the anolyte compartment after separation and cathode compartment product.
(2) in waste water, add anolyte and cathode deposition that step (1) obtains, make mg
2+: ammonia nitrogen in waste water: po
4 3-mol ratio is 1.1:1:1, and the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water.
(3) the magnesium ammonium phosphate crystalloid solution in recycling step (2) is in acid solution, and acidolysis 1h at 30 DEG C of temperature, is configured to the magnesium ammonium phosphate solution that massfraction is 15%.Be injected in anolyte compartment by magnesium ammonium phosphate solution, holding current density is 38ma/cm
2condition under, be separated 3h, obtain the anolyte compartment after separation and cathode compartment product, product drops into waste water circulation except ammonia.
Along with the increase of magnesium ammonium phosphate (be called for short MAP) acidolysis electrodialysis working cycle number of times, magnesium ammonium phosphate reclaims product circulation and sinks ammonia process and remove synthetic ammonia ammonia nitrogen in waste water effect and see Fig. 6; As we can see from the figure, the heavy ammonia rate of magnesium ammonium phosphate pyrolysis product circulation remains on 98%, and along with the increase of cycle index, heavy ammonia rate change is not obvious.
Claims (4)
1. reclaim a method for ammonia nitrogen in waste water, it is characterized in that, specifically comprise the following steps:
(1) the magnesium ammonium phosphate crystal reclaimed in wastewater treatment is dropped into acidic solution, obtain magnesium ammonium phosphate solution after carrying out acidolysis, be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 10 ~ 40ma/cm
2condition under, be separated 2 ~ 5h, obtain the anolyte compartment after separation and cathode compartment product;
(2) in waste water, add anolyte compartment and cathode compartment product that step (1) obtains, the ammonia nitrogen in anode and cathode product and waste water forms magnesium ammonium phosphate crystal, and precipitation is also separated with waste water;
(3) the magnesium ammonium phosphate dissolution of crystals in recycling step (2), in acid solution, is configured to the magnesium ammonium phosphate solution that massfraction is 5% ~ 70%; Be injected into by magnesium ammonium phosphate solution and be separated in room, pole, holding current density is 10 ~ 40ma/cm
2condition under, be separated 2 ~ 5h, obtain the anolyte after separation and cathode deposition, product drops into waste water circulation except ammonia.
2. reclaim the method for ammonia nitrogen in waste water according to claim 1, it is characterized in that: step (1) and the acidic solution described in (3) are one or both in sulfuric acid or hydrochloric acid, and the pH of acidic solution is not more than 4.
3. reclaim the method for ammonia nitrogen in waste water according to claim 1, it is characterized in that: step (1) and (3) middle magnesium ammonium phosphate liquid quality fraction are 5% ~ 70%.
4. reclaim the method for ammonia nitrogen in waste water according to claim 1, it is characterized in that: step (1) and (3) described acidolysis temperature are 10 DEG C ~ 60 DEG C, and the acidolysis time is 1 ~ 3 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098445A (en) * | 2017-04-26 | 2017-08-29 | 中国科学院城市环境研究所 | It is a kind of to utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater |
| CN108947012A (en) * | 2018-07-30 | 2018-12-07 | 中南大学 | A method of separating and recovering ammonia from ammonia nitrogen waste water |
| 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 |
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| JP2003039081A (en) * | 2001-07-30 | 2003-02-12 | Hitachi Ltd | Phosphorus recovery apparatus |
| JP2008229434A (en) * | 2007-03-19 | 2008-10-02 | Nittetsu Mining Co Ltd | Method for purifying ammonia nitrogen-containing wastewater |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098445A (en) * | 2017-04-26 | 2017-08-29 | 中国科学院城市环境研究所 | It is a kind of to utilize selective electrodialysis separating magnesium and the method reclaimed for waste water ammonium magnesium phosphate from seawater |
| CN107098445B (en) * | 2017-04-26 | 2020-08-04 | 中国科学院城市环境研究所 | Method for separating magnesium from seawater and recycling magnesium ammonium phosphate in wastewater by using selective electrodialysis |
| CN108947012A (en) * | 2018-07-30 | 2018-12-07 | 中南大学 | A method of separating and recovering ammonia from ammonia nitrogen waste water |
| CN108947012B (en) * | 2018-07-30 | 2021-10-22 | 中南大学 | Method for separating and recovering ammonia from ammonia nitrogen wastewater |
| 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 |
| CN110902898B (en) * | 2019-12-05 | 2023-06-23 | 浙江大学 | Device and method for removing nitrogen and phosphorus in sewage by magnesium anode electrodialysis method |
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