CN115504627A - Magnesium ammonium phosphate precipitation recovery device and technology based on ion exchange separation and enrichment - Google Patents
Magnesium ammonium phosphate precipitation recovery device and technology based on ion exchange separation and enrichment Download PDFInfo
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- CN115504627A CN115504627A CN202211113385.3A CN202211113385A CN115504627A CN 115504627 A CN115504627 A CN 115504627A CN 202211113385 A CN202211113385 A CN 202211113385A CN 115504627 A CN115504627 A CN 115504627A
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- ion exchange
- phosphorus
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- sewage
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- 238000005342 ion exchange Methods 0.000 title claims abstract description 163
- 238000011084 recovery Methods 0.000 title claims abstract description 100
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 title claims abstract description 69
- 229910052567 struvite Inorganic materials 0.000 title claims abstract description 67
- 238000000926 separation method Methods 0.000 title claims abstract description 32
- 238000001556 precipitation Methods 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 160
- 239000011574 phosphorus Substances 0.000 claims abstract description 159
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000010865 sewage Substances 0.000 claims abstract description 103
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000011282 treatment Methods 0.000 claims abstract description 33
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010802 sludge Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008929 regeneration Effects 0.000 claims description 154
- 238000011069 regeneration method Methods 0.000 claims description 154
- 239000007788 liquid Substances 0.000 claims description 119
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 94
- 239000011575 calcium Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000004062 sedimentation Methods 0.000 claims description 51
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 45
- 229910052791 calcium Inorganic materials 0.000 claims description 45
- -1 phosphorus ion Chemical class 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 206010021143 Hypoxia Diseases 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims 1
- 238000005137 deposition process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011221 initial treatment Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010841 municipal wastewater Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012492 regenerant Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000009294 enhanced biological phosphorus removal Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to an ammonium magnesium phosphate precipitation recovery device and process based on ion exchange separation and enrichment. The technology of the invention not only can break through the limit of the mol ratio of nitrogen and phosphorus in the sewage in a nitrogen diversion enrichment mode and realize high-efficiency low-cost phosphorus recovery in the form of magnesium ammonium phosphate, but also can solve the problems of sludge age contradiction between denitrification and phosphorus removal and carbon source competition in the traditional biological sewage treatment process, and realize the high-efficiency phosphorus recovery when the sewage reaches the discharge standard. Compared with the prior art, the method can be used for recovering phosphorus from town sewage and industrial wastewater and synchronously recovering partial nitrogen and magnesium.
Description
Technical Field
The invention relates to the technical field of environmental protection and sewage treatment, in particular to an ammonium magnesium phosphate precipitation recovery device and process based on ion exchange separation and enrichment.
Background
At present, the nitrogen and phosphorus removal of urban sewage is generally carried out by adopting a biological treatment technology, the contradiction of sludge age setting exists between biological phosphorus removal and nitrification, and the problem of carbon source competition exists between biological phosphorus removal and denitrification. Therefore, many sewage treatment plants will choose to use long sludge ages to ensure nitrification and to use carbon sources as much as possible for denitrification, and the effluent from biological treatment systems will usually contain higher phosphorus content. Therefore, the method can efficiently remove phosphorus from the effluent of the sewage biological treatment system and realize resource recovery, and is an effective means for preventing and controlling water eutrophication and an important way for realizing phosphorus resource recovery. However, at present, the effluent of the sewage biological treatment system is usually removed by adding aluminum salt or ferric salt to generate precipitate, and the high-value form recovery of phosphorus is not carried out. Among the various forms of phosphorus recovery, magnesium ammonium phosphate is the most economically valuable and promising target product. But the total phosphorus content in urban sewage is limited to be low, the molar ratio (10-30) of ammonia nitrogen (20-50 mg/L) and total phosphorus (3-6 mg/L) is far higher than the molar ratio (1. Therefore, the struvite precipitation method is generally used for recovering phosphorus from a high-concentration sludge dewatering liquid, and is not applied to a domestic sewage mainstream treatment system.
The current technical research and development can effectively solve the problems of high-efficiency removal and enrichment of phosphorus in domestic sewage. The traditional thought is that the phosphorus is enriched into the sludge by utilizing the enhanced biological phosphorus removal, and then the phosphorus is directionally recovered from the sludge dehydration or anaerobic digestion dehydration liquid or the sludge ash, but the phosphorus is recovered from the solid matters by converting the phosphorus in the matters into soluble positive-valence phosphorus for recovery. Efficient capture and concentration of phosphorus by ion exchange is a novel phosphorus enrichment method proposed in recent years. Chinese patent No. CN114684980A discloses a sewage treatment method, in the described treatment system respectively using acidic ion exchange resin to remove ammonia nitrogen and using basic ion exchange resin to remove total phosphorus so as to implement nitrogen and phosphorus removal in the sewage. Wherein the ion exchange resin total phosphorus removal unit comprises a sewage inlet pump, a water inlet valve, a phosphorus ion exchange column filled with ion exchange resin and a water outlet valve which are connected in sequence. The invention can effectively realize phosphorus capture, but does not mention a regeneration mode in the operation process and does not recover elements.
Meanwhile, much research work is currently focused on the recovery of phosphorus by precipitation and crystallization. The treatment system comprises an induced crystallization reactor and a solid-liquid separator, wherein the induced crystallization reactor comprises a sewage inlet pump, a seed crystal feeding box, an alkalinity feeding box, a pH tester and a water outlet valve, the solid-liquid separator comprises a solid-liquid separation device, a buffer zone, a water outlet valve and a water outlet box, wherein a water outlet of the induced crystallization reactor is communicated with the solid-liquid separation device, so that crystals settled in the buffer zone can return to the induced crystallization reactor again. However, the method is suitable for wastewater with high phosphorus content. In addition, the phosphorus concentration in the effluent of the precipitation reactor is difficult to stably reach the first grade A standard of pollutant discharge Standard of municipal wastewater treatment plant (GB 18918-2002) limited by the solubility product constant of the chemical precipitation method, which limits the application of the technology in domestic sewage.
Therefore, the phosphorus recovery from domestic sewage by magnesium ammonium phosphate method is urgent to solve the phosphorus concentration problem and reduce the cost of ammonium salt and magnesium salt used for precipitation. Meanwhile, the phosphorus concentration and recovery technology needs to be organically coupled with the existing sewage treatment technology to ensure that all indexes of treated effluent such as Total Nitrogen (TN), total Phosphorus (TP), chemical Oxygen Demand (COD) and the like stably reach the standard.
Disclosure of Invention
The invention aims to solve the problems that domestic sewage is difficult to directly recover phosphorus and the molar ratio of nitrogen to phosphorus is high, and provides an ammonium magnesium phosphate precipitation recovery device and process based on ion exchange separation and enrichment. The technology of the invention not only can break through the limit of the mol ratio of nitrogen and phosphorus in the sewage in a nitrogen diversion enrichment mode and realize high-efficiency low-cost phosphorus recovery in the form of magnesium ammonium phosphate, but also can solve the problems of sludge age contradiction between denitrification and phosphorus removal and carbon source competition in the traditional biological sewage treatment process, and realize the high-efficiency phosphorus recovery when the sewage reaches the discharge standard.
The purpose of the invention can be realized by the following technical scheme:
the utility model provides a magnesium ammonium phosphate deposits recovery unit based on ion exchange separation enrichment, includes mainstream sewage treatment pipeline and sidestream regeneration liquid pipeline, mainstream sewage treatment pipeline is including ammonium ion exchange unit, oxygen deficiency/aerobic reactor and the phosphorus ion exchange unit who connects gradually, sidestream regeneration liquid pipeline is including the regeneration liquid reserve tank of built-in regeneration liquid, and this regeneration liquid reserve tank connects gradually through the pipeline ammonium ion exchange unit, calcium recovery sedimentation tank phosphorus ion exchange unit and magnesium ammonium phosphate sedimentation tank, the delivery port of magnesium ammonium phosphate sedimentation tank still returns to be connected regeneration liquid reserve tank.
Furthermore, the mainstream sewage treatment pipeline also comprises a sewage inlet pump and a water inlet pretreatment unit which are sequentially connected and positioned at the front end of the ammonium ion exchange unit.
Furthermore, the sewage inlet pump also leads another branch to be directly connected with the anoxic/aerobic reactor.
In a further aspect, the wastewater to be treated is town wastewater and industrial wastewater.
In addition, the water inlet pretreatment unit adopts chemically enhanced primary treatment.
Furthermore, the anoxic/aerobic reactor comprises an anoxic tank, an aerobic tank and a solid-liquid separation unit which are sequentially arranged along the sewage treatment direction, sludge at the bottom of the solid-liquid separation unit flows back to the anoxic tank, and mixed liquid in the aerobic tank flows back to the anoxic tank.
In the above still further aspect, the solid-liquid separation unit is a secondary sedimentation tank or a membrane module.
Furthermore, an ammonium ion exchange water inlet valve and an ammonium ion exchange water outlet valve are respectively arranged at the front end and the rear end of the ammonium ion exchange unit.
Furthermore, a water inlet valve of the phosphorus ion exchange unit and a water outlet valve of the phosphorus ion exchange unit are respectively arranged at the front end and the rear end of the phosphorus ion exchange unit.
Further, the working mode of the ammonium ion exchange unit comprises an up-flow mode or a down-flow mode.
Furthermore, the working mode of the phosphorus ion exchange unit is an up-flow mode or a down-flow mode.
Furthermore, a regeneration liquid inlet pump and a regeneration liquid inlet valve are arranged between the regeneration liquid storage tank and the ammonium ion exchange unit.
Furthermore, a regenerated liquid outlet valve is arranged between the ammonium ion exchange unit and the calcium recovery sedimentation tank.
Further, the calcium recovery sedimentation tank is also provided with a calcium recovery doser.
Furthermore, a phosphorus ion exchange regeneration liquid water outlet valve is further arranged on the phosphorus ion exchange unit, and a pH adjusting box and a magnesium source doser are further arranged on the magnesium ammonium phosphate sedimentation tank.
In addition, the invention also provides a magnesium ammonium phosphate precipitation recovery process based on ion exchange separation and enrichment, which is implemented by adopting the magnesium ammonium phosphate precipitation recovery device, and the recovery process comprises the following steps:
s1, feeding a part of sewage to be treated into an ammonium ion exchange unit, and rapidly capturing ammonia nitrogen in the sewage by using an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit and the other part of the sewage to be treated are converged into an anoxic/aerobic bioreactor;
s3, treating the sewage by using an anoxic/aerobic bioreactor, and then, allowing the sewage to enter a phosphorus ion exchange unit, wherein a phosphorus ion exchanger rapidly captures phosphorus in the sewage to obtain purified sewage and discharging the purified sewage;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and emptying the ammonium ion exchange unit and the phosphorus ion exchange unit for regeneration;
s5, during regeneration, sending the regenerated liquid in the regenerated liquid storage tank into an ammonium ion exchange unit to complete regeneration of an ammonium ion exchanger, then entering a calcium recovery sedimentation tank, adding a calcium recovery precipitant into the calcium recovery sedimentation tank, stirring, and settling after full reaction;
s6, enabling the effluent from the upper part of the calcium recovery sedimentation tank to enter a phosphorus ion exchange unit to complete regeneration of a phosphorus ion exchanger, then enabling the effluent to flow into an ammonium magnesium phosphate sedimentation tank, adding a pH regulator into the ammonium magnesium phosphate sedimentation tank and supplementing a magnesium source, stirring, fully reacting and then settling, wherein the obtained precipitate is magnesium ammonium phosphate and is recovered.
Further, in the step S1, the flow ratio of the wastewater to be treated is determined according to the molar ratio of the nitrogen and phosphorus concentrations in the wastewater.
Further, in step S1, the ammonium ion exchanger is selected from one or more of natural zeolite, modified zeolite, molecular sieve, vermiculite, montmorillonite, ion exchange resin, and the like.
Further, in step S1, the empty column residence time (EBCT) of the sewage to be treated in the ammonium ion exchange unit is 1-300min.
Further, in step S2, the pH of the inlet water of the anoxic/aerobic bioreactor is controlled to be 6.0-9.0.
Further, in step S2, the water inlet temperature of the anoxic/aerobic bioreactor is controlled to be 10-40 ℃.
Further, in step S2, the sludge age (SRT) of the anoxic/aerobic bioreactor is 5-500d.
Further, in step S2, the Hydraulic Retention Time (HRT) of the anoxic/aerobic bioreactor is 0.5-48h.
Further, in step S2, the phosphorus ion exchanger is selected from one or more of activated carbon, metal oxide, ion exchange resin, molecular sieve, zeolite, and the like.
Further, in the step S2, the empty column retention time of the treated sewage in the phosphorus ion exchange unit is 1-600min.
Further, in step S5, the regeneration liquid includes sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate solution or a mixture thereof.
Further, in the step S5, the concentration of the regeneration liquid is 0.01-200g/L.
Further, in step S5, the pH of the regeneration liquid reserve tank is controlled to 6.0 to 2.0.
Further, in step S5, the ammonium ion exchanger regeneration mode includes concurrent regeneration or countercurrent regeneration.
Furthermore, in step S5, the regeneration time of the regeneration liquid to the ammonium ion exchanger is 0.1-72h.
Further, in step S5, the calcium recovery precipitant is selected from one or more of carbonate, bicarbonate, and polyphosphate fluoride.
Further, in the step S5, the hydraulic retention time of the calcium recovery sedimentation tank is 0.1-24h.
Further, in step S6, the regeneration mode of the phosphorus ion exchanger includes concurrent regeneration or countercurrent regeneration.
Furthermore, in step S6, the regeneration time of the regeneration liquid to the phosphorus ion exchanger is 0.1-72h.
Further, in step S6, the pH adjusting agent is selected from one or more of sodium hydroxide, potassium hydroxide, lime, magnesium oxide, sodium carbonate, sodium bicarbonate, magnesium hydroxide, hydrochloric acid, sulfuric acid, and the like.
The reaction principle of the invention is as follows:
anoxic/aerobic biological treatment unit: the anoxic/aerobic biological treatment converts nitrogen in the sewage into nitrogen for removal through 3 processes of ammoniation, aerobic nitrification and anoxic denitrification; at the same time, in the aerobic unit, the organic matter is converted into CO by supplying oxygen 2 And (4) removing.
Ammonium ion exchange unit: removal of NH from wastewater by ion exchange with solid ammonium ion exchangers 4 + And enabling the effluent to meet the requirements of relevant discharge standards, wherein the ion exchange reaction is shown as a formula (1):
wherein A is + Is an ammonium ion exchanger surface exchangeable ion, Z - Is in an ammonium ion exchanger structure.
Calcium and magnesium in the wastewater can be trapped by the ion exchange unit while the ammonium ion exchange is carried out, see formulas (2) and (3)
2A + Z - +Ca 2+ →Ca 2+ (Z - ) 2 +2A + (2)
2A + Z - +Mg 2+ →Mg 2+ (Z - ) 2 +2A + (3)
An ammonia nitrogen regeneration unit: the regeneration unit utilizes the positive ions in the regeneration liquid to react NH on the surface of the ammonium ion exchanger 4 + 、Ca 2+ And Mg 2+ The regeneration reaction is shown as formula (4):
Ca 2+ (Z - ) 2 +2M + →2M + Z - +Ca 2+ (5)
Mg 2+ (Z - ) 2 +2M + →2M + Z - +Mg 2+ (6)
wherein M is + Is the cation in the regenerating liquid. The regeneration process is endothermic reaction, and heating the regeneration liquid is beneficial to realizing rapid and efficient regeneration.
A phosphorus ion exchange unit: the solid phosphorus ion exchanger removes phosphorus in the sewage through ion exchange, so that the effluent meets the requirements of relevant discharge standards, and the ion exchange reaction is shown as formula (7):
B 3+ (C - ) 3 +PO 4 3- →B 3+ PO 4 3- +3C - (7)
wherein the content of the first and second substances,C - is surface exchangeable ions of a phosphorus ion exchanger, B 3+ Is a phosphorus ion exchanger structure.
A phosphorus regeneration unit: the regeneration unit exchanges phosphorus ions on the surface of the ion exchanger into the regeneration liquid by utilizing anions in the regeneration liquid to realize the regeneration of the phosphorus ion exchanger. The regeneration reaction is shown in formula (8):
B 3+ PO 4 3- +3D - →B 3+ (D - ) 3 +PO 4 3- (8)
wherein D is - Is the anion in the phosphorus regeneration liquid.
The invention aims to synchronously regenerate partial ammonium ion exchanger and phosphorus ion exchanger by using the same regeneration liquid. The invention aims to carry out chemical precipitation on Ca in the ammonia nitrogen regeneration liquid 2+ The phosphorus is recycled, and the influence on the purity of the phosphorus recycled product caused by the inflow of the phosphorus into a subsequent processing unit is avoided. Reuse of PO in regenerated liquid 4 3- 、NH 4 + 、Mg 2+ And part of the added Mg (OH) 2 And (4) recovering magnesium ammonium phosphate. The principle of each unit reaction is as follows.
A calcium ion recovery unit: adding the precipitation agent into the calcium ion recovery unit, using CaCO 3 Form of recovering Ca 2+ . See formula (9):
ammonium magnesium phosphate recovery unit: to regenerate NH in liquid 4 + As nitrogen source, mg 2+ And recovered Mg (OH) 2 As a magnesium source, magnesium ammonium phosphate was synthesized. See formula (10):
Mg 2+ +PO 4 3- +NH 4 + +6H 2 O→MgNH 4 PO 4 ·6H 2 O (10)
the combined process based on ammonium ion exchange/regeneration-phosphorus ion exchange/regeneration provided by the invention solves the problem that phosphorus is difficult to recover due to low phosphorus concentration and high nitrogen-phosphorus molar ratio of town sewageBy means of NH 4 + And PO 4 3- The positive valence state and the negative valence state of the nitrogen-phosphorus composite regenerant are different, so that the nitrogen and phosphorus can be synchronously enriched in the same regenerant. NH in wastewater 4 + And PO 4 3- Removal can be achieved by an ion exchange unit, yielding NH 4 + The concentration of N, TN and TP can reach the first grade A emission standard of pollutants emission Standard of municipal wastewater treatment plant (GB 18918-2002). At the time of regeneration, due to NH 4 + And PO 4 3- The regeneration of the catalyst requires cations and anions respectively, so that the regeneration agent can meet the requirements of the regeneration of the catalyst by adopting a salt. After the regeneration of the ammonium ion exchanger is completed, calcium ions in the regeneration liquid are converted into precipitate recovery by adding a calcium recovery precipitator, and meanwhile, the purity of magnesium ammonium phosphate can be ensured. After completion of the regeneration of the phosphorus ion exchanger, the pH and Mg (OH) are adjusted 2 And generating magnesium ammonium phosphate to realize synchronous recovery of nitrogen and phosphorus. At the same time, the recovery of magnesium ammonium phosphate also reduces NH in the regenerated liquid 4 + And PO 4 3- Concentration of NH in the regeneration liquid 4 + And PO 4 3- The regeneration of the phosphorus ion exchanger and the ammonium ion exchanger is inhibited, and the recycling of the regeneration liquid and the high-efficiency regeneration of the ion exchanger are realized. In addition, a foundation is laid for resource recycling application of nitrogen and phosphorus pollutants in the wastewater.
The invention can be used for recovering phosphorus from town sewage and industrial wastewater and synchronously recovering partial nitrogen and magnesium, and compared with the prior art, the invention has the following advantages:
(1) PIR module can remove PO under short HRT fast 4 3- Has the advantages of small occupied area and water outlet PO 4 3- The concentration is low;
(2) By means of sewage diversion, ammonia nitrogen and magnesium in sewage are recycled by using an ammonium ion exchange/regeneration module, the problem that ammonia nitrogen is difficult to treat after phosphorus is recycled due to unbalanced nitrogen-phosphorus molar ratio in sewage is avoided, and meanwhile, part of magnesium source is recycled from sewage to compensate for the cost of struvite precipitation agent;
(3) In the calcium ion precipitation and recovery process, the metal cations are supplemented for the regenerated liquid while the calcium ion recovery agent is added, so that the concentration of the metal cations in the regenerated liquid is maintained, and the high-efficiency regeneration is ensured;
(4) The recovery of magnesium ammonium phosphate effectively reduces NH in the regenerated liquid 4 + And PO 4 3- Concentration of NH in the regeneration liquid 4 + And PO 4 3- The regeneration of the phosphorus ion exchanger and the ammonium ion exchanger is inhibited, so that the recycling of the regeneration liquid and the high-efficiency regeneration of the ion exchanger are realized;
(5) The invention realizes the enrichment and recovery of phosphorus through ion exchange, and effectively solves the problems of sludge age contradiction of nitrification and biological phosphorus removal and carbon source competition of denitrification and anaerobic phosphorus release faced by the domestic sewage nitrogen and phosphorus removal. Meanwhile, the denitrification effect of domestic sewage, particularly sewage with a low carbon-nitrogen ratio, can be effectively enhanced by separating and denitrifying part of sewage ammonium and effectively supplementing a denitrification carbon source.
Drawings
FIG. 1 is a schematic flow chart of a magnesium ammonium phosphate precipitation recovery technique based on ion exchange separation and enrichment according to the present invention;
FIG. 2 is a schematic diagram of the magnesium ammonium phosphate recovery technique of the present invention;
FIG. 3 is a schematic diagram of the water quality of a pilot experiment run for a period of 30 days in example 2;
FIG. 4 is an X-ray diffraction pattern of struvite recovered in example 2;
FIG. 5 is a scanning electron micrograph of recovered magnesium ammonium phosphate of example 2;
FIG. 6 is a graphical representation of the variation of N, P and Mg concentrations during mainstream ion exchange and sidestream struvite recovery in example 3.
The reference numbers illustrate: 1. the system comprises a water inlet pretreatment unit, 2, an ammonium ion exchange unit, 3, an anoxic/aerobic bioreactor, 4, a phosphorus ion exchange unit, 5, a calcium recovery sedimentation tank, 6, an ammonium magnesium phosphate sedimentation tank, 7, a regeneration liquid storage tank, 8, a calcium recovery doser, 9, a pH adjusting tank, 10, a magnesium source doser, 11, a sewage inlet pump, 12, a side flow regeneration liquid delivery pump, 13, an ammonium ion exchange inlet valve, 14, an ammonium ion exchange outlet valve, 15, an ammonium ion exchange regeneration liquid inlet valve, 16, an ammonium ion exchange regeneration liquid outlet valve, 17, a phosphorus ion exchange unit inlet valve, 18, a phosphorus ion exchange outlet valve, 19, a phosphorus ion exchange regeneration liquid outlet valve, 20 an anoxic tank, 21, an aerobic tank and 22 solid-liquid separation unit.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following embodiments or examples, unless otherwise specified, raw materials, or equipment structures, or processing techniques are all conventional commercially available products, conventional commercially available equipment, or conventional processing techniques in the art.
The utility model provides a magnesium ammonium phosphate deposits recovery unit based on ion exchange separation enrichment, includes mainstream sewage treatment pipeline and sidestream regeneration liquid pipeline, mainstream sewage treatment pipeline is including ammonium ion exchange unit 2, oxygen deficiency aerobic reactor 3 and the phosphorus ion exchange unit 4 that connect gradually, sidestream regeneration liquid pipeline is including the regeneration liquid storage tank 7 of built-in regeneration liquid, and this regeneration liquid storage tank 7 connects gradually through the pipeline ammonium ion exchange unit 2, calcium recovery sedimentation tank 5 phosphorus ion exchange unit 4 and magnesium ammonium phosphate sedimentation tank 6, the delivery port of magnesium ammonium phosphate sedimentation tank 6 still returns to be connected regeneration liquid storage tank 7.
In a specific embodiment, the mainstream sewage treatment pipeline further comprises a sewage inlet pump 11 and an inlet water pretreatment unit 1 which are sequentially connected with each other at the front end of the ammonium ion exchange unit 2.
In a specific embodiment, the sewage inlet pump 11 further introduces a branch to directly connect with the anoxic/aerobic reactor 3.
In a still further aspect, the wastewater to be treated is town sewage and industrial wastewater.
In addition, the water inlet pretreatment unit 1 adopts chemically enhanced primary treatment.
In a specific embodiment, the anoxic/aerobic reactor 3 comprises an anoxic tank 20, an aerobic tank 21 and a solid-liquid separation unit 22 which are sequentially arranged along the sewage treatment direction, a sludge return pipe is further arranged at the bottom of the solid-liquid separation unit 22 and is connected with the anoxic tank 20 in a return mode, and the aerobic tank 21 is provided with a mixed liquid return pipe and is connected with the anoxic tank in a return mode.
In the above still further aspect, the solid-liquid separation unit is a secondary sedimentation tank or a membrane module.
In a specific embodiment, the front end and the rear end of the ammonium ion exchange unit 2 are respectively provided with an ammonium ion exchange water inlet valve 13 and an ammonium ion exchange water outlet valve 14.
In a specific embodiment, the front end and the rear end of the phosphorus ion exchange unit 4 are respectively provided with a phosphorus ion exchange unit water inlet valve 17 and a phosphorus ion exchange unit water outlet valve 18.
In a specific embodiment, the mode of operation of the ammonium ion exchange unit 2 comprises an upflow mode or a downflow mode.
In a specific embodiment, the phosphorus ion exchange unit 4 operates in an upflow mode or a downflow mode.
In a specific embodiment, a regeneration liquid inlet pump 12 and a regeneration liquid inlet valve 15 are further arranged between the regeneration liquid storage tank 7 and the ammonium ion exchange unit 2.
In a specific embodiment, a regeneration liquid outlet valve 16 is further arranged between the ammonium ion exchange unit 2 and the calcium recovery and precipitation tank 5.
In a specific embodiment, the calcium recovery and sedimentation tank 5 is further provided with a calcium recovery doser 8.
In a specific embodiment, a phosphorus ion exchange regeneration liquid outlet valve 19 is further arranged on the phosphorus ion exchange unit 4, and a pH adjusting tank 9 and a magnesium source doser 10 are further arranged on the magnesium ammonium phosphate sedimentation tank 6.
In addition, the invention also provides a magnesium ammonium phosphate precipitation recovery process based on ion exchange separation and enrichment, which is implemented by adopting the magnesium ammonium phosphate precipitation recovery device, and the recovery process comprises the following steps:
s1, feeding a part of sewage to be treated into an ammonium ion exchange unit 2, and rapidly capturing ammonia nitrogen in the sewage by using an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit 2 and the other part of the sewage to be treated are converged into an anoxic/aerobic bioreactor 3;
s3, treating the sewage by the anoxic/aerobic bioreactor 3, then, allowing the sewage to enter a phosphorus ion exchange unit 4, and rapidly capturing phosphorus in the sewage by using a phosphorus ion exchanger to obtain purified sewage and discharging the purified sewage;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and emptying the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 for regeneration;
s5, during regeneration, sending the regenerated liquid in the regenerated liquid storage box 7 into the ammonium ion exchange unit 2 to complete regeneration of an ammonium ion exchanger, then entering a calcium recovery sedimentation tank 5, adding a calcium recovery precipitant into the calcium recovery sedimentation tank 5, stirring, and settling after sufficient reaction;
s6, enabling the effluent from the upper part of the calcium recovery sedimentation tank 5 to enter a phosphorus ion exchange unit 4 to complete regeneration of a phosphorus ion exchanger, then enabling the effluent to flow into the magnesium ammonium phosphate sedimentation tank 6, adding a pH regulator into the magnesium ammonium phosphate sedimentation tank 6 and supplementing a magnesium source, stirring, fully reacting and then settling, wherein the obtained precipitate is magnesium ammonium phosphate and is recovered.
In a specific embodiment, in step S1, the flow ratio of the wastewater to be treated is determined according to a molar ratio of nitrogen to phosphorus concentration in the wastewater.
In a specific embodiment, in step S1, the ammonium ion exchanger is selected from one or more of natural zeolite, modified zeolite, molecular sieve, vermiculite, montmorillonite, ion exchange resin, and the like.
In a specific embodiment, in step S1, EBCT of the wastewater to be treated in the ammonium ion exchange unit 2 is 1-300min.
In a specific embodiment, in step S2, the pH of the influent to the anoxic/aerobic bioreactor 3 is controlled to be between 6.0 and 9.0.
In a specific embodiment, in step S2, the temperature of the influent to the anoxic/aerobic bioreactor 3 is controlled to be in the range of 10-40 ℃.
In a specific embodiment, the SRT of the anoxic/aerobic bioreactor 3 in step S2 is between 5 and 500d.
In a specific embodiment, the HRT of the anoxic/aerobic bioreactor 3 in step S2 is 0.5-48h.
In a specific embodiment, in step S2, the phosphorus ion exchanger is selected from one or more of activated carbon, metal oxide, ion exchange resin, molecular sieve, zeolite, and the like.
In a specific embodiment, in step S2, the residence time of the treated wastewater in the phosphorus ion exchange unit 4 is 1-600min.
In a specific embodiment, in step S5, the regeneration liquid includes sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate solution or a mixture thereof.
In a specific embodiment, in step S5, the concentration of the regeneration liquid is 0.01-200g/L.
In a specific embodiment, in step S5, the pH of the regeneration liquid storage tank 7 is controlled to 6.0-2.0.
In a specific embodiment, in step S5, the ammonium ion exchanger regeneration mode comprises concurrent regeneration or countercurrent regeneration.
In a specific embodiment, in step S5, the regeneration liquid is used for regenerating the ammonium ion exchanger for 0.1 to 72 hours.
In a specific embodiment, in step S5, the calcium recovery precipitant is selected from one or more of carbonate, bicarbonate, polyphosphate fluoride.
In a specific embodiment, in step S5, the hydraulic retention time of the calcium recovery and sedimentation basin 5 is 0.1 to 24 hours.
In a specific embodiment, in step S6, the regeneration mode of the phosphorus ion exchanger comprises concurrent regeneration or countercurrent regeneration.
In a specific embodiment, in step S6, the regeneration time of the phosphorus ion exchanger by the regeneration liquid is 0.1-72h.
In a specific embodiment, in step S6, the pH adjusting agent is selected from one or more of sodium hydroxide, potassium hydroxide, lime, magnesium oxide, sodium carbonate, sodium bicarbonate, magnesium hydroxide, hydrochloric acid, sulfuric acid, and the like.
The above embodiments will be described in more detail with reference to specific examples.
Example 1
A magnesium ammonium phosphate precipitation recovery technology based on ion exchange separation and enrichment is shown in figure 1, and the mainstream technology comprises a pretreatment module, an ammonium ion exchange module, an anoxic/aerobic bioreactor and a phosphorus ion exchange module. The sidestream phosphorus recovery process comprises an ammonia nitrogen regeneration module, a calcium ion recovery module, a phosphorus regeneration module and an ammonium magnesium phosphate precipitation recovery module. The main flow middle pretreatment module comprises a sewage inlet pump 11 and an inlet pretreatment unit 1 which are connected in sequence. The ammonium ion exchange module comprises an ammonium ion exchange unit water inlet valve 13, an ammonium ion exchange unit 2 filled with an ion exchanger and a water outlet valve 14 which are connected in sequence. The anoxic/aerobic bioreactor 3 comprises an anoxic tank 20, an aerobic tank 21 and a solid-liquid separation unit 22. The phosphorus ion exchange module comprises a phosphorus ion exchange unit water inlet valve 17, a phosphorus ion exchange unit 4 filled with phosphorus ion exchangers and a phosphorus ion exchange unit water outlet valve 18.
In the sidestream phosphorus recovery process, the ammonia nitrogen regeneration module comprises a regeneration liquid storage box 7, a regeneration liquid inlet pump 12, a regeneration liquid inlet valve 15, an ammonium ion exchange unit 2 and a regeneration liquid outlet valve 16 which are sequentially connected. The calcium recovery module comprises a calcium recovery sedimentation tank 5 and a calcium recovery doser 8. The phosphorus regeneration module comprises a phosphorus ion exchange unit 4 and a phosphorus ion exchange regeneration liquid water outlet valve 19 which are sequentially connected, and the water inlet of the phosphorus ion exchange regeneration liquid is controlled by a regeneration liquid water outlet valve 16 of the ammonium ion exchange unit. The magnesium ammonium phosphate recovery module comprises a magnesium ammonium phosphate sedimentation tank 6, a pH adjusting box 9 and a magnesium source doser 10.
The method comprises the following specific steps: the sewage to be treated enters the water inlet pretreatment unit 1 from the water inlet pump 11, the pretreated outlet water enters the ammonium ion exchange unit 2 through the water outlet valve 13, after the ammonia nitrogen in the sewage is rapidly captured by the ammonium ion exchanger, the sewage and the sewage to be treated are converged into the anoxic/aerobic bioreactor 3 through the water outlet valve 13 of the ammonium ion exchange unit 2, the sewage enters the final phosphorus ion exchange unit 4 after treatment, and the phosphorus in the sewage is rapidly captured by the phosphorus ion exchanger and then is discharged. And after the set ion exchange time is reached, the sewage inlet pump is closed, and the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 are emptied for regeneration.
During regeneration, the regeneration liquid in the regeneration liquid storage box 7 enters the ammonium ion exchange unit 2 through a regeneration liquid inlet pump 12 and a regeneration liquid inlet valve 15, the ammonium ion exchange unit 2 enters the calcium recovery sedimentation tank 5 through a regeneration liquid outlet valve 16 after regeneration is finished, a calcium recovery chemical adding device 8 adds a calcium recovery precipitating agent into the calcium recovery sedimentation tank 5 and stirs the calcium recovery precipitating agent, the precipitate is discharged through a mud bucket after full reaction, the water discharged from the calcium recovery sedimentation tank 5 enters the phosphorus ion exchange unit 4 and then enters the ammonium magnesium phosphate sedimentation tank 6 through a phosphorus ion exchange regeneration liquid outlet valve 19, a pH adjusting box 7 and a magnesium source chemical adding device 8 add a pH adjusting agent into the ammonium magnesium phosphate sedimentation tank 6 and supplement a magnesium source, the magnesium source is stirred and is settled after full reaction, and finally the precipitate is discharged through the mud bucket and is a phosphorus recovery product and then flows back to the regeneration liquid storage box 7 to form a cyclic regeneration treatment system.
And (3) closing the regeneration liquid inlet pump 12 after the regeneration is finished, completely returning the regeneration liquid to the regeneration liquid storage tank 7, finishing the regeneration, and standing the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 until the next operation.
Example 2
COD, TN and NH of inlet water of certain sewage treatment plant 4 + The concentration of N and TP is 180, 27.5, 25.0 and 3.0mg/L respectively, and the treated product needs to reach GB18918-2002 first-grade A standard (COD)<50mg/L，NH 4 + -N<5mg/L，TP<0.5 mg/L). The pilot test research is carried out by adopting the process, the water treatment amount of the pilot test is 1 ton/day, and the time is 30 days.
According to the measurement and calculation of the mole ratio of nitrogen and phosphorus, 6% of sewage to be shunted enters a 'pretreatment + AIR' process. The pretreatment unit adopts chemical strengthening primary treatment, the coagulation and flocculation units adopt concentric cylinder design, the volumes are 0.08L and 0.42L respectively, and the volume of the sedimentation tank is 1.25L. The coagulant and the flocculant are aluminum sulfate and anionic Polyacrylamide (PAM), the adding amount is 30mg/L and 0.3mg/L respectively, and the coagulation stirring speed is 200r/min. The pretreated effluent enters an ammonium ion exchange unit 2 through a water outlet valve 13, the volume of the ammonium ion exchange unit 2 is 2.5L, natural zeolite is filled in the ammonium ion exchange unit 2, and the adsorption operation time is 20h. And 2 groups of ion exchange units are arranged for standby.
And the rest 94 percent of sewage enters an anoxic/aerobic reactor 3, the total HRT is 6h, the effective volumes of an anoxic tank and an aerobic tank are respectively 83L and 167L, and the volume of a secondary sedimentation tank is 167L. The sludge age of the anoxic/aerobic bioreactor is set to be 20 days, the internal reflux ratio is 200 percent, and the external reflux ratio is 100 percent. The effluent of the anoxic/aerobic bioreactor enters a phosphorus ion exchange unit 4, the exchange unit is filled with anion exchange resin, the volume of the exchange unit is 21L, and the device is additionally provided with 2 groups for use. Average effluent COD, TN, NH of the process during operation 4 + The N and TP concentrations were 20.2, 6.0, 0.3 and 0.1mg/L, respectively (FIG. 3).
And after the preset running time is reached, the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 are emptied, and the sewage is pumped into the standby unit by the sewage inlet pump 11 to continuously treat the sewage. The regeneration liquid adopts sodium chloride solution, the concentration of sodium ions is 20g/L, and the volume of the regeneration liquid is 50L. Sodium carbonate is added into a calcium recovery sedimentation tank 5 as a precipitator, and the supernatant enters a phosphorus ion exchange unit 4 to regenerate anion exchange resin. After regeneration is finished, NH in regeneration liquid 4 + The concentration of N was 47.9mg/L, the concentration of phosphorus was 61.2mg/L, and the concentration of magnesium ion was 8.9mg/L. The regenerated solution was introduced into a magnesium ammonium phosphate precipitation tank 6, the pH was adjusted to 9.5, magnesium hydroxide was added, and 385.9g of magnesium ammonium phosphate was recovered per day. The recovered magnesium ammonium phosphate meets the standards as set forth by the Shaoxing City standards Association in T/SXAS 005-2020, and is described in detail in Table 1. The XRD and SEM characterization of magnesium ammonium phosphate obtained is shown in fig. 4, 5. The magnesium ammonium phosphate crystal obtained in the invention has a typical rhombic prism structure, has different surface numbers, has few impurities attached to the surface, and is a precipitated struvite crystalThe body reaches a length of 40-50 μm. EDS analysis showed that the resulting crystals had a Mg: N: P = 1.01.
TABLE 1 comparison of the indexes of magnesium ammonium phosphate and magnesium ammonium phosphate standards recovered from wastewater
Note: measured as a dried sample.
Example 3
Aiming at 300mg/L of COD, 30mg/L of TN and NH 4 + The inlet water of a certain sewage plant with 25mg/L of N, 3.5mg/L of TP, 33.5mg/L of magnesium ion and 44.5mg/L of calcium ion needs to reach GB18918-2002 first-grade A standard (COD is COD) after treatment<50mg/L，NH 4 + -N<5mg/L，TP<0.5 mg/L). The pilot-scale research is carried out by adopting the technology of the invention, the water treatment amount is 2 tons/day, and the time is 60 days.
This example is substantially the same as example 2, with the volumes of the coagulation and flocculation units in the pretreatment unit being 0.21 and 1.04L, respectively, and the volume of the sedimentation tank being 3.13L. The ammonium ion exchanger in the ammonium ion exchange unit 2 was a cation exchange resin having a volume of 4.7L and EBCT of 45min, and group 2 of ion exchange units were prepared for use. The volume of the anoxic/aerobic bioreactor 2 is 667L, the HRT is 8h, and the volume of the secondary sedimentation tank is 500L. The phosphorus ion exchanger in the phosphorus ion exchange reactor 4 was anion exchange resin with a volume of 42L, EBCT of 30min, and 2 groups were used. During the pilot test, average effluent COD, TN and NH 4 + The concentration of N and TP is respectively 25.8, 7.0, 0.5 and 0.2mg/L, and meets the first grade A standard in GB 18918-2002.
The regeneration liquid adopts 50g/L sodium chloride solution, and the volume is 100L. The calcium recovery precipitant is sodium carbonate, and the magnesium source is magnesium hydroxide. The molar ratio of N/Mg/P was controlled at 1.0. The supernatant from the struvite crystallization reactor flows into the regeneration liquid storage tank 7 for the next cycle. 562.9g of magnesium ammonium phosphate were recovered daily during the pilot plant. The recovered magnesium ammonium phosphate meets the standards as promulgated by the standards association of shaoxing, T/SXAS 005-2020, and is described in detail in table 2.
TABLE 2 index comparison of magnesium ammonium phosphate recovered from wastewater with magnesium ammonium phosphate standards
Note: measured as a dried sample.
In addition, it should be noted that the specific embodiments described in the present specification may differ in the shape of the components, the names of the components, and the like. All equivalent or simple changes in the structure, characteristics and principles of the invention which are described in the patent conception are included in the protection scope of the invention. Various modifications, additions and substitutions for the specific embodiments described herein may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (10)
1. The utility model provides a magnesium ammonium phosphate deposits recovery unit based on ion exchange separation enrichment, its characterized in that, includes mainstream sewage treatment pipeline and sidestream regeneration liquid pipeline, mainstream sewage treatment pipeline is including ammonium ion exchange unit (2), oxygen deficiency/aerobic reaction ware (3) and phosphorus ion exchange unit (4) that connect gradually, sidestream regeneration liquid pipeline is including built-in regeneration liquid's regeneration liquid reserve tank (7), and this regeneration liquid reserve tank (7) connect gradually through the pipeline ammonium ion exchange unit (2), calcium recovery sedimentation tank (5) phosphorus ion exchange unit (4) and magnesium ammonium phosphate sedimentation tank (6), the delivery port of magnesium ammonium phosphate sedimentation tank (6) still returns and connects regeneration liquid reserve tank (7).
2. The struvite precipitation recovery device based on ion exchange separation and enrichment of claim 1, characterized in that the main stream sewage treatment pipeline further comprises a sewage inlet pump (11) and an inlet water pretreatment unit (1) which are sequentially connected with each other at the front end of the ammonium ion exchange unit (2);
the sewage inlet pump (11) is also provided with another branch which is directly connected with the anoxic/aerobic reactor (3).
3. The magnesium ammonium phosphate precipitation recovery device based on ion exchange separation and enrichment according to claim 1, characterized in that the anoxic/aerobic reactor (3) comprises an anoxic tank (20), an aerobic tank (21) and a solid-liquid separation unit (22) which are sequentially arranged along the sewage treatment direction, a sludge return pipe is further arranged at the bottom of the solid-liquid separation unit (22) and is connected with the anoxic tank (20) in a return way, and the aerobic tank (21) is provided with a mixed liquid return pipe and is connected with the anoxic tank (20) in a return way.
4. The magnesium ammonium phosphate precipitation recovery device based on ion exchange separation enrichment according to the claim 1, characterized in that the front and back ends of the ammonium ion exchange unit (2) are respectively provided with an ammonium ion exchange water inlet valve (13) and an ammonium ion exchange water outlet valve (14);
and the front end and the rear end of the phosphorus ion exchange unit (4) are respectively provided with a phosphorus ion exchange unit water inlet valve (17) and a phosphorus ion exchange unit water outlet valve (18).
5. The struvite precipitation recovery device based on ion exchange separation enrichment according to claim 1, characterized in that the ammonium ion exchange unit (2) works in an upflow mode or a downflow mode;
the working mode of the phosphorus ion exchange unit (4) is an up-flow mode or a down-flow mode.
6. The magnesium ammonium phosphate precipitation recovery device based on ion exchange separation and enrichment of claim 1, characterized in that a regeneration liquid inlet pump (12) and a regeneration liquid inlet valve (15) are further arranged between the regeneration liquid storage tank (7) and the ammonium ion exchange unit (2);
a regenerated liquid water outlet valve (16) is also arranged between the ammonium ion exchange unit (2) and the calcium recovery sedimentation tank (5);
the calcium recovery sedimentation tank (5) is also provided with a calcium recovery doser (8).
7. The magnesium ammonium phosphate precipitation recovery device based on ion exchange separation enrichment according to claim 1, characterized in that a phosphorus ion exchange regeneration liquid outlet valve (19) is further arranged on the phosphorus ion exchange unit (4), and a pH adjusting tank (9) and a magnesium source doser (10) are further arranged on the magnesium ammonium phosphate sedimentation tank (6).
8. A magnesium ammonium phosphate precipitation recovery process based on ion exchange separation and enrichment, which is implemented by adopting the magnesium ammonium phosphate precipitation recovery device of any one of claims 1-7, and is characterized in that the recovery process comprises the following steps:
s1, feeding a part of sewage to be treated into an ammonium ion exchange unit (2), and rapidly capturing ammonia nitrogen in the sewage by using an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit (2) and the other part of the sewage to be treated are converged into an anoxic/aerobic bioreactor (3);
s3, treating the sewage by the anoxic/aerobic bioreactor (3), and then, allowing the sewage to enter a phosphorus ion exchange unit (4), wherein a phosphorus ion exchanger rapidly captures phosphorus in the sewage to obtain purified sewage and discharging the purified sewage;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and emptying the ammonium ion exchange unit (2) and the phosphorus ion exchange unit (4) for regeneration;
s5, during regeneration, sending the regenerated liquid in the regenerated liquid storage box (7) into the ammonium ion exchange unit (2) to complete regeneration of an ammonium ion exchanger, then entering a calcium recovery sedimentation tank (5), adding a calcium recovery precipitant into the calcium recovery sedimentation tank (5), stirring, and settling after full reaction;
s6, enabling the water discharged from the upper part of the calcium recovery sedimentation tank (5) to enter a phosphorus ion exchange unit (4) to complete regeneration of a phosphorus ion exchanger, then flowing into the magnesium ammonium phosphate sedimentation tank (6), adding a pH regulator into the magnesium ammonium phosphate sedimentation tank (6) and supplementing a magnesium source, stirring, fully reacting and settling, wherein the obtained precipitate is magnesium ammonium phosphate and is recovered.
9. The process of claim 8, wherein in step S1, the flow ratio of the wastewater to be treated is determined according to the molar ratio of nitrogen and phosphorus concentrations in the wastewater;
in the step S1, the ammonium ion exchanger is selected from one or more of natural zeolite, modified zeolite, molecular sieve, vermiculite, montmorillonite, ion exchange resin and the like;
in the step S1, the staying time of the sewage to be treated in the empty column of the ammonium ion exchange unit (2) is 1-300min;
in the step S2, the pH value of the inlet water of the anoxic/aerobic bioreactor (3) is controlled to be 6.0-9.0;
in the step S2, the water inlet temperature of the anoxic/aerobic bioreactor (3) is controlled to be 10-40 ℃;
in the step S2, the sludge age of the anoxic/aerobic bioreactor (3) is 5-500 days;
in the step S2, the hydraulic retention time of the anoxic/aerobic bioreactor (3) is 0.5-48h;
in the step S2, the phosphorus ion exchanger is selected from one or more of activated carbon, metal oxide, ion exchange resin, molecular sieve, zeolite and the like;
in the step S2, the residence time of the treated sewage in the empty column of the phosphorus ion exchange unit (4) is 1-600min.
10. The deposition and recovery process of magnesium ammonium phosphate based on ion exchange separation and enrichment as claimed in claim 8, wherein in step S5, the regeneration liquid comprises sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate solution or their mixture;
in the step S5, the concentration of the regeneration liquid is 0.01-200g/L;
in the step S5, the pH value of the regeneration liquid storage tank (7) is controlled to be 6.0-2.0;
in step S5, the regeneration mode of the ammonium ion exchanger comprises concurrent regeneration or countercurrent regeneration;
in the step S5, the regeneration time of the regeneration liquid to the ammonium ion exchanger is 0.1-72h;
in step S5, the calcium recovery precipitant is one or more selected from carbonate, bicarbonate and polyphosphate fluoride;
in the step S5, the hydraulic retention time of the calcium recovery sedimentation tank (5) is 0.1-24h;
in the step S6, the regeneration mode of the phosphorus ion exchanger comprises forward flow regeneration or reverse flow regeneration;
in the step S6, the regeneration time of the regeneration liquid to the phosphorus ion exchanger is 0.1-72h;
in step S6, the pH adjuster is one or more selected from sodium hydroxide, potassium hydroxide, lime, magnesium oxide, sodium carbonate, sodium bicarbonate, magnesium hydroxide, hydrochloric acid, sulfuric acid, and the like.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423314A (en) * | 2008-12-03 | 2009-05-06 | 北京师范大学 | High efficiency denitrification, phosphorus removal and phosphorus resource recovery composite for urban sewage |
| WO2018107740A1 (en) * | 2016-12-14 | 2018-06-21 | 江南大学 | Wastewater nitrogen and phosphorus removal device and application thereof |
| CN108217839A (en) * | 2018-03-14 | 2018-06-29 | 安徽水韵环保股份有限公司 | A kind for the treatment of technology of the method for Nitrogen-and Phosphorus-containing sewage treatment and recovery |
| CN112093981A (en) * | 2020-09-10 | 2020-12-18 | 上海电力大学 | Sewage treatment device and process for synchronously and efficiently removing pollutants and comprehensively recycling pollutants |
| CN113860431A (en) * | 2021-11-11 | 2021-12-31 | 上海电力大学 | Device and process for relieving ion exchanger pollution |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423314A (en) * | 2008-12-03 | 2009-05-06 | 北京师范大学 | High efficiency denitrification, phosphorus removal and phosphorus resource recovery composite for urban sewage |
| WO2018107740A1 (en) * | 2016-12-14 | 2018-06-21 | 江南大学 | Wastewater nitrogen and phosphorus removal device and application thereof |
| CN108217839A (en) * | 2018-03-14 | 2018-06-29 | 安徽水韵环保股份有限公司 | A kind for the treatment of technology of the method for Nitrogen-and Phosphorus-containing sewage treatment and recovery |
| CN112093981A (en) * | 2020-09-10 | 2020-12-18 | 上海电力大学 | Sewage treatment device and process for synchronously and efficiently removing pollutants and comprehensively recycling pollutants |
| CN113860431A (en) * | 2021-11-11 | 2021-12-31 | 上海电力大学 | Device and process for relieving ion exchanger pollution |
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