CN115504627B - Magnesium ammonium phosphate precipitation recovery device and process based on ion exchange separation enrichment - Google Patents
Magnesium ammonium phosphate precipitation recovery device and process based on ion exchange separation enrichment Download PDFInfo
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- CN115504627B CN115504627B CN202211113385.3A CN202211113385A CN115504627B CN 115504627 B CN115504627 B CN 115504627B CN 202211113385 A CN202211113385 A CN 202211113385A CN 115504627 B CN115504627 B CN 115504627B
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- ion exchange
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- regeneration
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- 238000005342 ion exchange Methods 0.000 title claims abstract description 165
- 238000011084 recovery Methods 0.000 title claims abstract description 101
- 229910052567 struvite Inorganic materials 0.000 title claims abstract description 82
- 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 81
- 238000001556 precipitation Methods 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title abstract description 29
- 230000008929 regeneration Effects 0.000 claims abstract description 160
- 238000011069 regeneration method Methods 0.000 claims abstract description 160
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 155
- 239000011574 phosphorus Substances 0.000 claims abstract description 154
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000010865 sewage Substances 0.000 claims abstract description 119
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- 238000011282 treatment Methods 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010802 sludge Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 118
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- 238000004062 sedimentation Methods 0.000 claims description 58
- 239000011575 calcium Substances 0.000 claims description 51
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 44
- 229910052791 calcium Inorganic materials 0.000 claims description 44
- -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
- 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 15
- 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
- 238000004064 recycling Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application 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
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 239000002244 precipitate 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
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000011221 initial treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 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
- 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
- 238000003426 chemical strengthening reaction Methods 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
- 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
- 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
- 230000001172 regenerating effect Effects 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
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 239000012492 regenerant Substances 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 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
- 239000013078 crystal Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 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 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
- 238000011020 pilot scale process Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 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
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002351 wastewater Substances 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 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
- 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
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012530 fluid Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005185 salting out 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
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
Abstract
The invention relates to a magnesium ammonium phosphate precipitation recovery device and process based on ion exchange separation enrichment, which are used for recovering magnesium ammonium phosphate by a mainstream shunt nitrogen separation enrichment-phosphorus ion exchange enrichment-sidestream regeneration precipitation technology, so that synchronous enrichment of nitrogen and phosphorus in the same regenerant is realized, and a carbon source can be supplemented by a sewage backflow anoxic/aerobic denitrification reactor after shunt nitrogen separation. The technology of the invention not only can break through the limitation of the mole ratio of nitrogen and phosphorus in sewage in a nitrogen diversion enrichment mode and realize the efficient and low-cost phosphorus recovery in the form of magnesium ammonium phosphate, but also can solve the problems of sludge age contradiction and carbon source competition of denitrification and dephosphorization in the traditional biological sewage treatment process, and realize the efficient phosphorus recovery while the sewage is discharged up to the standard. Compared with the prior art, the invention can be used for phosphorus recovery of town sewage and industrial wastewater, and synchronously recovers part of nitrogen and magnesium.
Description
Technical Field
The invention relates to the technical field of environmental protection and sewage treatment, in particular to a magnesium ammonium phosphate precipitation recovery device and process based on ion exchange separation and enrichment.
Background
At present, biological treatment technology is generally adopted for denitrification and dephosphorization of town sewage, the contradiction between sludge age setting exists between biological dephosphorization and nitrification, and the carbon source competition problem exists between biological dephosphorization and denitrification. Therefore, many sewage treatment plants choose to use long sludge ages to ensure nitrification and use carbon sources as much as possible for denitrification, with biological treatment system effluent typically having a higher phosphorus content. Therefore, the method is an effective means for preventing and controlling water eutrophication and is an important way for realizing phosphorus resource recovery. However, the effluent of the current 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 performed. Among the various phosphorus recovery forms, magnesium ammonium phosphate is the most economically valuable and promising target product for application. But is limited by the fact that the total phosphorus content in town sewage is low, the molar ratio (10-30) of ammonia nitrogen (20-50 mg/L) to total phosphorus (3-6 mg/L) is far higher than the molar ratio (1:1) required by magnesium ammonium phosphate precipitation, and an additional magnesium source is required. Therefore, the magnesium ammonium phosphate precipitation method is generally used for phosphorus recovery in high-concentration sludge dewatering liquid, and is not applied to a main flow treatment system of the domestic sewage.
The problems of efficient removal and enrichment of phosphorus in domestic sewage can be effectively solved by the research and development of the current technology. The traditional thinking is that the phosphorus is enriched into the sludge by utilizing the reinforced biological phosphorus removal, and then directionally recovered from the sludge dewatering or anaerobic digestion dewatering liquid or the sludge ash, but the phosphorus recovered from the solid substance needs to be subjected to complicated pretreatment, and the phosphorus in the substance is converted into the soluble positive-valence phosphorus for recovery. Efficient trapping and concentration of phosphorus by ion exchange is a new phosphorus enrichment method proposed in recent years. Chinese patent CN114684980a discloses a sewage treatment method, in which the acidic ion exchange resin is used to remove ammonia nitrogen and total phosphorus from alkaline ion exchange resin, so as to implement denitrification and dephosphorization in sewage. The ion exchange resin total phosphorus removal unit comprises a sewage water 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 trapping, but the regeneration mode is not mentioned in the operation process, and the elements are not recovered.
Meanwhile, much research work is currently focused on the recovery of phosphorus by precipitation crystallization. As disclosed in chinese patent CN104973723a, the treatment system comprises an induced crystallization reactor and a solid-liquid separator, the induced crystallization reactor comprises a sewage water inlet pump, a seed crystal feeding box, an alkalinity dosing 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 tank, wherein the water outlet of the induced crystallization reactor is communicated with the solid-liquid separation device, so that the crystal precipitated in the buffer zone can be returned to the induced crystallization reactor again. But the method is often suitable for wastewater with higher phosphorus content. In addition, the solubility product constant of the chemical precipitation method is limited, and the phosphorus concentration in the effluent of the precipitation reactor is difficult to stably reach the first-level A standard of pollutant emission Standard of urban wastewater treatment plant (GB 18918-2002), which limits the application of the technology in domestic wastewater.
Therefore, there is a need to solve the problem of phosphorus concentration and to reduce the cost of ammonium and magnesium salts used for precipitation in the recovery of phosphorus from domestic sewage by magnesium ammonium phosphate. Meanwhile, the phosphorus concentration recovery technology needs to be organically coupled with the existing sewage treatment technology, so that various indexes such as Total Nitrogen (TN), total Phosphorus (TP), chemical Oxygen Demand (COD) and the like of the treated effluent are ensured to reach the standard stably.
Disclosure of Invention
The invention aims to solve the problems that domestic sewage is difficult to directly recycle phosphorus and the mole ratio of nitrogen to phosphorus is high, and provides a magnesium ammonium phosphate precipitation recycling device and process based on ion exchange separation and enrichment. The technology of the invention not only can break through the limitation of the mole ratio of nitrogen and phosphorus in sewage in a nitrogen diversion enrichment mode and realize the efficient and low-cost phosphorus recovery in the form of magnesium ammonium phosphate, but also can solve the problems of sludge age contradiction and carbon source competition of denitrification and dephosphorization in the traditional biological sewage treatment process, and realize the efficient phosphorus recovery while the sewage is discharged up to the standard.
The aim of the invention can be achieved 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/good oxygen reactor and the phosphorus ion exchange unit that connects gradually, sidestream regeneration liquid pipeline includes 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 connect the regeneration liquid reserve tank.
Further, the main stream sewage treatment pipeline also comprises a sewage water inlet pump and a water inlet pretreatment unit which are positioned at the front end of the ammonium ion exchange unit and are connected in sequence.
Further, the sewage water inlet pump is also provided with a branch which is directly connected with the anoxic/aerobic reactor.
The sewage to be treated is town sewage and industrial wastewater.
The above further, the inlet water pretreatment unit adopts a chemical strengthening primary treatment.
Further, 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, wherein sludge at the bottom of the solid-liquid separation unit flows back to the anoxic tank, and mixed liquid of the aerobic tank flows back to the anoxic tank.
The solid-liquid separation unit is a secondary sedimentation tank or a membrane component.
Further, the front end and the rear end of the ammonium ion exchange unit are respectively provided with an ammonium ion exchange water inlet valve and an ammonium ion exchange water outlet valve.
Further, the front end and the rear end of the phosphorus ion exchange unit are respectively provided with a phosphorus ion exchange unit water inlet valve and a phosphorus ion exchange unit water outlet valve.
Further, the operation mode of the ammonium ion exchange unit comprises an up-flow mode or a down-flow mode.
Further, the phosphorus ion exchange unit works in an up-flow or down-flow mode.
Further, a regeneration liquid water inlet pump and a regeneration liquid water inlet valve are arranged between the regeneration liquid reserve tank and the ammonium ion exchange unit.
Further, a regeneration liquid water 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.
Further, the phosphorus ion exchange unit is also provided with a phosphorus ion exchange regeneration liquid outlet valve, and the magnesium ammonium phosphate sedimentation tank is also provided with a pH adjusting box and a magnesium source doser.
In addition, the invention also provides a magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment, which is implemented by adopting the magnesium ammonium phosphate precipitation recovery device, and comprises the following steps:
s1, sending a part of sewage to be treated into an ammonium ion exchange unit, and rapidly capturing ammonia nitrogen in the sewage by an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit and the other part of sewage to be treated are led into an anoxic/aerobic bioreactor;
s3, after the sewage is treated by the anoxic/aerobic bioreactor, the sewage enters a phosphorus ion exchange unit, and phosphorus in the sewage is rapidly captured by a phosphorus ion exchanger, so that purified sewage is obtained and discharged;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and evacuating the ammonium ion exchange unit and the phosphorus ion exchange unit for regeneration;
s5, during regeneration, the regenerated liquid in the regenerated liquid storage tank is sent to an ammonium ion exchange unit to complete the regeneration of the ammonium ion exchanger, then the regenerated liquid enters a calcium recovery sedimentation tank, a calcium recovery sedimentation agent is added into the calcium recovery sedimentation tank, and the mixture is stirred and settled after full reaction;
s6, the water discharged from the upper part of the calcium recovery sedimentation tank enters a phosphorus ion exchange unit to complete the regeneration of the phosphorus ion exchanger, then flows into a magnesium ammonium phosphate sedimentation tank, adds a pH regulator into the magnesium ammonium phosphate sedimentation tank and supplements a magnesium source, and the obtained precipitate is magnesium ammonium phosphate and is recovered after stirring and full reaction.
Further, in step S1, the flow ratio of the sewage to be treated is determined according to the molar ratio of the concentration of nitrogen and phosphorus in the sewage.
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 residence time (EBCT) of the sewage to be treated in the empty column of 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 the 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 0.5-48 hours.
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 residence time of the treated sewage in the empty column of the phosphorus ion exchange unit is 1-600min.
Further, in step S5, the regeneration solution 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 be 6.0-2.0.
Further, in step S5, the regeneration mode of the ammonium ion exchanger includes downstream regeneration or countercurrent regeneration.
Further, in step S5, the regeneration time of the regeneration liquid on 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, 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 downstream regeneration or countercurrent regeneration.
Further, in step S6, the regeneration time of the regenerating solution on the phosphorus ion exchanger is 0.1-72h.
Further, in step S6, the pH adjustor 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: anoxic/aerobic biological treatment removes nitrogen in sewage into nitrogen through 3 processes of ammoniation, aerobic nitrification and anoxic denitrification; simultaneously, in an aerobic unit, organic matters are converted into CO through oxygen supply 2 And (5) removing.
An ammonium ion exchange unit: solid ammonium ion exchanger for removing NH in sewage by ion exchange 4 + The effluent meets the requirements of relevant emission standards, and the ion exchange reaction is shown in the formula (1):
wherein A is + Ion exchangeable for the surface of the ammonium ion exchanger, Z - Is an ammonium ion exchanger structure.
At the same time of ammonium ion exchange, calcium and magnesium in the sewage can be trapped by an ion exchange unit, and the formulas (2) and (3) are shown
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 uses the cation in the regeneration liquid to make NH on the surface of the ammonium ion exchanger 4 + 、Ca 2+ And Mg (magnesium) 2+ Exchange into regeneration liquid to realize regeneration of ammonium ion exchanger, the regeneration reaction is shown in 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 a cation in the regeneration liquid. The regeneration process is endothermic reaction, and the heating of the regeneration liquid is beneficial to realizing rapid and efficient regeneration.
Phosphorus ion exchange unit: the solid phosphorus ion exchanger removes phosphorus in sewage through ion exchange, so that effluent reaches the requirements of relevant emission standards, and the ion exchange reaction is shown in formula (7):
B 3+ (C - ) 3 +PO 4 3- →B 3+ PO 4 3- +3C - (7)
wherein C is - Ion exchangeable for the surface of the phosphorus ion exchanger, B 3+ Is a phosphorus ion exchanger structure.
Phosphorus regeneration unit: the regeneration unit utilizes anions in the regeneration liquid to exchange the phosphorus ions on the surface of the ion exchanger into the regeneration liquid, thereby realizing 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 an anion in the phosphorus regeneration liquid.
The invention aims to synchronously regenerate partial ammonium ion exchanger and phosphorus ion exchanger by adopting the same regeneration liquid. The invention aims to chemically precipitate Ca in ammonia nitrogen regeneration liquid 2+ And recycling is carried out, so that the influence of the inflow of the phosphorus into a subsequent treatment unit on the purity of the phosphorus recycling product is avoided. Reuse of PO in regeneration liquid 4 3- 、NH 4 + 、Mg 2+ And part of additional Mg (OH) 2 And (5) generating magnesium ammonium phosphate for recovery. The reaction principle of each unit is as follows.
Calcium ion recovery unit: adding the precipitation agent into a calcium ion recovery unit to obtain CaCO 3 Form (c) of Ca recovery 2+ . The specific reaction formula is shown in formula (9):
magnesium ammonium phosphate recovery unit: by NH in the regenerating liquid 4 + As a nitrogen source, mg 2+ And recovered Mg (OH) 2 As a magnesium source, magnesium ammonium phosphate was synthesized. The reaction is shown in 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 solves the problem that phosphorus is difficult to recycle due to low phosphorus concentration in town sewage and high nitrogen-phosphorus molar ratio, and utilizes NH 4 + And PO (PO) 4 3- The synchronous enrichment of nitrogen and phosphorus in the same regenerant is realized by the positive and negative valence state difference of the regenerant. NH in sewage 4 + And PO (PO) 4 3- Can be removed by an ion exchange unit, and the effluent NH 4 + The concentrations of N, TN and TP can reach the first grade A emission standard of pollutant emission standard of urban sewage treatment plant (GB 18918-2002). During regeneration, due to NH 4 + And PO (PO) 4 3- The regeneration of (a) requires cations and anions respectively, so that the regeneration agent can meet the regeneration requirements of both by adopting one salt. After the regeneration of the ammonium ion exchanger is completed, calcium ions in the regenerated liquid are converted into precipitate for recovery by adding a calcium recovery precipitant, and meanwhile, the purity of magnesium ammonium phosphate can be ensured. After the regeneration of the phosphorus ion exchanger is completed, the pH and Mg (OH) are adjusted 2 And magnesium ammonium phosphate is generated, so that synchronous recovery of nitrogen and phosphorus is realized. At the same time, the NH in the regenerated liquid is reduced by recycling magnesium ammonium phosphate 4 + And PO (PO) 4 3- Concentration of NH in the regeneration liquid 4 + And PO (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 efficient regeneration of the ion exchanger are realized. In addition, a foundation is laid for recycling and applying the nitrogen and phosphorus pollutants in the wastewater.
The invention can be used for phosphorus recovery of town sewage and industrial wastewater, and synchronously recovers part of nitrogen and magnesium, and compared with the prior art, the invention has the following advantages:
(1) PIR module can get rid of PO fast under short HRT 4 3- Has small occupied area and PO of effluent 4 3- The concentration is low;
(2) The ammonia nitrogen and magnesium in the sewage are recovered by utilizing an ammonium ion exchange/regeneration module in a sewage diversion mode, so that the problem that the ammonia nitrogen is difficult to treat after phosphorus recovery due to the unbalanced nitrogen-phosphorus molar ratio in the sewage is avoided, and meanwhile, the cost of the struvite precipitation medicament is compensated by recovering part of magnesium sources from the sewage;
(3) In the calcium ion precipitation recovery process, the metal cations are supplemented for the regeneration liquid while the calcium ion recovery medicament is added, so that the concentration of the metal cations in the regeneration liquid is maintained, and high-efficiency regeneration is ensured;
(4) The recovery of magnesium ammonium phosphate effectively reduces NH in the regenerated liquid 4 + And PO (PO) 4 3- Concentration of NH in the regeneration liquid 4 + And PO (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 ion exchange are realizedEfficient regeneration of the replacement agent;
(5) The invention realizes the enrichment and recovery of phosphorus through ion exchange, and effectively solves the problems of contradiction between nitrification and biological phosphorus removal mud age and carbon source competition of denitrification and anaerobic phosphorus release in the denitrification and phosphorus removal of domestic sewage. Meanwhile, partial flow of the sewage is used for separating and denitrifying ammonium, so that a denitrifying carbon source is effectively supplemented, and the denitrification effect of domestic sewage, particularly sewage with low carbon nitrogen ratio, can be effectively enhanced.
Drawings
FIG. 1 is a schematic flow chart of a magnesium ammonium phosphate precipitation recovery technique based on ion exchange separation enrichment;
FIG. 2 is a schematic diagram of the magnesium ammonium phosphate recovery technique of the present invention;
FIG. 3 is a schematic diagram of water quality for a 30 day pilot plant run in example 2;
FIG. 4 is an X-ray diffraction pattern of the magnesium ammonium phosphate recovered in example 2;
FIG. 5 is a scanning electron microscope image of the magnesium ammonium phosphate recovered in example 2;
FIG. 6 is a graph showing the change in N, P and Mg concentration during the main stream ion exchange and side stream magnesium ammonium phosphate recovery in example 3.
Reference numerals illustrate: 1. the device 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, a magnesium ammonium 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 water inlet pump, 12, a side flow regeneration liquid conveying pump, 13, an ammonium ion exchange water inlet valve, 14, an ammonium ion exchange water outlet valve, 15, an ammonium ion exchange regeneration liquid water inlet valve, 16, an ammonium ion exchange regeneration liquid water outlet valve, 17, a phosphorus ion exchange unit water inlet valve, 18, a phosphorus ion exchange water outlet valve, 19, a phosphorus ion exchange regeneration liquid water outlet valve, 20 anoxic tanks, 21, an aerobic tank and 22 solid-liquid separation units.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following embodiments or examples, unless otherwise indicated, materials, or equipment configurations, or processing techniques, are all indicated as conventional commercial products, conventional commercial 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/good oxygen reactor 3 and the phosphorus ion exchange unit 4 that connect gradually, sidestream regeneration liquid pipeline includes the regeneration liquid reserve tank 7 of built-in regeneration liquid, this regeneration liquid reserve 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 connect regeneration liquid reserve tank 7.
In a specific embodiment, the main flow sewage treatment pipeline further comprises a sewage water inlet pump 11 and a water inlet pretreatment unit 1 which are positioned at the front end of the ammonium ion exchange unit 2 and are sequentially connected.
In a specific embodiment, the sewage inlet pump 11 is further connected to the anoxic/aerobic reactor 3 directly by a branch.
The sewage to be treated is town sewage and industrial wastewater.
Further to the above, the inlet water pretreatment unit 1 adopts a chemically strengthened primary treatment.
In a specific embodiment, the anoxic/aerobic reactor 3 includes an anoxic tank 20, an aerobic tank 21 and a solid-liquid separation unit 22 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 manner, and the aerobic tank 21 is provided with a mixed liquor return pipe and is connected with the anoxic tank in a return manner.
The solid-liquid separation unit is a secondary sedimentation tank or a membrane component.
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 ammonium ion exchange unit 2 is operated in an up-flow or down-flow manner.
In a specific embodiment, the phosphorus ion exchange unit 4 operates in an up-flow or down-flow mode.
In a specific embodiment, a regeneration liquid water inlet pump 12 and a regeneration liquid water inlet valve 15 are further arranged between the regeneration liquid reserve tank 7 and the ammonium ion exchange unit 2.
In a specific embodiment, a regeneration liquid outlet valve 16 is further disposed between the ammonium ion exchange unit 2 and the calcium recovery sedimentation tank 5.
In a specific embodiment, the calcium recovery sedimentation tank 5 is further provided with a calcium recovery doser 8.
In a specific embodiment, the phosphorus ion exchange unit 4 is further provided with a phosphorus ion exchange regeneration liquid outlet valve 19, and the magnesium ammonium phosphate sedimentation tank 6 is further provided with a pH adjusting box 9 and a magnesium source doser 10.
In addition, the invention also provides a magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment, which is implemented by adopting the magnesium ammonium phosphate precipitation recovery device, and comprises the following steps:
s1, sending a part of sewage to be treated into an ammonium ion exchange unit 2, and rapidly capturing ammonia nitrogen in the sewage by an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit 2 and the other part of sewage to be treated are led into the anoxic/aerobic bioreactor 3;
s3, after the sewage is treated by the anoxic/aerobic bioreactor 3, the sewage enters the phosphorus ion exchange unit 4, and the phosphorus ion exchanger rapidly captures phosphorus in the sewage to obtain purified sewage and discharges the purified sewage;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and evacuating the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 for regeneration;
s5, during regeneration, the regenerated liquid in the regenerated liquid storage tank 7 is sent to the ammonium ion exchange unit 2 to complete the regeneration of the ammonium ion exchanger, then the regenerated liquid enters the calcium recovery sedimentation tank 5, and the calcium recovery sedimentation tank 5 is added with a calcium recovery sedimentation agent and stirred, and is settled after full reaction;
s6, the water discharged from the upper part of the calcium recovery sedimentation tank 5 enters the phosphorus ion exchange unit 4 to complete the regeneration of the phosphorus ion exchanger, then flows into the magnesium ammonium phosphate sedimentation tank 6, adds a pH regulator into the magnesium ammonium phosphate sedimentation tank 6 and supplements a magnesium source, and the magnesium ammonium phosphate sedimentation tank is stirred, fully reacts and then is settled, and the obtained precipitate is the magnesium ammonium phosphate and is recovered.
In a specific embodiment, in step S1, the flow rate ratio of the sewage to be treated is determined according to the molar ratio of the concentration of nitrogen and phosphorus in the sewage.
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, the EBCT of the sewage to be treated in the ammonium ion exchange unit 2 is 1 to 300min.
In a specific embodiment, in step S2, the pH of the inlet water of the anoxic/aerobic bioreactor 3 is controlled to be 6.0-9.0.
In a specific embodiment, in step S2, the inlet water temperature of the anoxic/aerobic bioreactor 3 is controlled between 10 ℃ and 40 ℃.
In a specific embodiment, in step S2, the anoxic/aerobic bioreactor 3 has an SRT of 5-500d.
In a specific embodiment, in step S2, the HRT of the anoxic/aerobic bioreactor 3 is 0.5-48 hours.
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 sewage in the column of the phosphorus ion exchange unit 4 is 1 to 600min.
In a specific embodiment, in step S5, the regeneration solution 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 reserve tank 7 is controlled to be 6.0-2.0.
In a specific embodiment, in step S5, the ammonium ion exchanger regeneration mode includes either concurrent regeneration or countercurrent regeneration.
In a specific embodiment, in step S5, the regeneration time of the ammonium ion exchanger by the regeneration liquid is 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 sedimentation tank 5 is 0.1 to 24 hours.
In a specific embodiment, in step S6, the phosphorus ion exchanger regeneration mode includes downstream 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 to 72 hours.
In a specific embodiment, in step S6, the pH adjuster 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 are described in more detail below in connection with specific examples.
Example 1
A magnesium ammonium phosphate precipitation recovery technology based on ion exchange separation enrichment, a process flow chart is shown in figure 1, and the main stream process comprises a pretreatment module, an ammonium ion exchange module, an anoxic/aerobic bioreactor and a phosphorus ion exchange module. The side-stream phosphorus recovery process comprises an ammonia nitrogen regeneration module, a calcium ion recovery module, a phosphorus regeneration module and a magnesium ammonium phosphate precipitation recovery module. The main stream 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 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 a phosphorus ion exchanger and a phosphorus ion exchange unit water outlet valve 18.
In the side-stream phosphorus recovery process, the ammonia nitrogen regeneration module comprises a regeneration liquid reserve tank 7, a regeneration liquid water inlet pump 12, a regeneration liquid water inlet valve 15, an ammonium ion exchange unit 2 and a regeneration liquid water outlet valve 16 which are connected in sequence. 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 outlet valve 19 which are connected in sequence, and the water inlet of the phosphorus ion exchange regeneration liquid is controlled by a regeneration liquid 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 inlet pretreatment unit 1 from the inlet pump 11, the pretreated effluent enters the ammonium ion exchange unit 2 through the outlet valve 13, the ammonium ion exchanger rapidly captures ammonia nitrogen in the sewage, the sewage and the sewage to be treated are gathered into the anoxic/aerobic bioreactor 3 through the outlet valve 13 of the ammonium ion exchange unit 2, the sewage enters the last phosphorus ion exchange unit 4 after being treated, and the phosphorus ion exchanger rapidly captures phosphorus in the sewage and then discharges water. After the set ion exchange time is reached, the sewage water 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 reserve tank 7 enters the ammonium ion exchange unit 2 through the regeneration liquid water inlet pump 12 and the regeneration liquid water inlet valve 15, the ammonium ion exchange unit 2 enters the calcium recovery sedimentation tank 5 through the regeneration liquid water outlet valve 16 after regeneration is finished, the calcium recovery dosing device 8 adds the calcium recovery sedimentation agent into the calcium recovery sedimentation tank 5 and stirs, sedimentation is carried out after full reaction, finally the sediment is discharged through a mud bucket, the water discharged from the calcium recovery sedimentation tank 5 enters the phosphorus ion exchange unit 4, then the phosphorus ion exchange regeneration liquid water enters the ammonium magnesium phosphate sedimentation tank 6 through the phosphorus ion exchange regeneration liquid water outlet valve 19, the pH regulator is added into the ammonium magnesium phosphate sedimentation tank 6 through the pH regulator 7 and the magnesium source dosing device 8, and the magnesium source is supplemented, stirs, sedimentation is carried out after full reaction, finally the sediment is discharged through the mud bucket, the sediment is the phosphorus recovery product, and then the sediment flows back to the regeneration liquid reserve tank 7 to form a recycling treatment system.
After the regeneration is finished, the regeneration liquid water inlet pump 12 is closed, the regeneration liquid is completely returned to the regeneration liquid storage tank 7, the regeneration is finished, and the ammonium ion exchange unit 2 and the phosphorus ion exchange unit 4 are stood until the next operation.
Example 2
Inflow COD, TN, NH of sewage treatment plant 4 + The concentrations of-N, TP are 180 mg/L, 27.5 mg/L, 25mg/L and 3.0mg/L respectively, and the treated water is required to reach the first grade A standard (COD) of GB18918-2002<50mg/L，NH 4 + -N<5mg/L，TP<0.5 mg/L). The pilot-scale study is carried out by adopting the process, the pilot-scale treatment water quantity is 1 ton/day, and the duration is 30 days.
According to the measurement and calculation of the molar ratio of nitrogen to phosphorus, 6% of sewage needs to be split into a pretreatment and AIR process. The pretreatment unit adopts chemical strengthening primary treatment, the coagulation and flocculation unit adopts concentric cylinder design, the volumes are respectively 0.08L and 0.42L, 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 an effluent valve 13, the volume of the ion exchange unit 2 is 2.5L, natural zeolite is filled in the ion exchange unit, and the adsorption running time is 20h. 2 groups of ion exchange units are additionally arranged for standby.
The remaining 94% of sewage enters an anoxic/aerobic reactor 3, the total HRT is 6 hours, the effective volumes of an anoxic tank and an aerobic tank are 83L and 167L respectively, and the volume of a secondary sedimentation tank is 167L. The sludge age of the anoxic/aerobic bioreactor is set to 20d, 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 is 21L, and 2 groups of the anion exchange resin are additionally arranged for standby. During operation, average effluent COD, TN, NH of the process 4 + N and TP concentrations were 20.2, 6.0, 0.3 and 0.1mg/L, respectively (FIG. 3).
After the preset operation 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 sodium ion concentration is 20g/L, and the volume of the regeneration liquid is 50L. Sodium carbonate is used as a precipitator to be added into a calcium recovery sedimentation tank 5, and supernatant fluid enters a phosphorus ion exchange unit 4 to regenerate anion exchange resin. After regeneration is finished, NH in the regenerated liquid 4 + The N concentration was 47.9mg/L, the phosphorus concentration was 61.2mg/L, and the magnesium ion concentration was 8.9mg/L. The regenerated liquid was flowed 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 every day. The recovered magnesium ammonium phosphate meets the standards promulgated by the Shaoxing standards Association, T/SXAS 005-2020, as detailed in Table 1. XRD and SEM characterizations of the obtained magnesium ammonium phosphate are shown in fig. 4, 5. The magnesium ammonium phosphate crystal obtained by the invention has a typical rhombic prism structure and different surface numbers, the surface of the magnesium ammonium phosphate crystal is less in attached impurities, and the precipitated struvite crystal reaches the length of 40-50 mu m. EDS analysis shows that Mg: N: p=1.01:0.99:1.02 in the resulting crystals is close to the theoretical value of struvite.
Table 1 index comparison of recovered magnesium ammonium phosphate and magnesium ammonium phosphate Standard in Sewage
Note that: based on the dried sample.
Example 3
For COD 300mg/L, TN 30mg/L, NH 4 + The water inlet of a sewage plant with 25mg/L, TP of N, 3.5mg/L of magnesium ion concentration, 33.5mg/L and 44.5mg/L of calcium ion is treated to reach the first grade A standard GB18918-2002 (COD)<50mg/L，NH 4 + -N<5mg/L，TP<0.5 mg/L). Pilot-scale studies were carried out using the technique of the invention with a water treatment capacity of 2 tons/day for 60 days.
The present example was similar to example 2, and the volumes of the coagulation and flocculation units in the pretreatment unit in this example were 0.21 and 1.04L, respectively, and the volume of the sedimentation tank was 3.13L. The ammonium ion exchanger in the ammonium ion exchange unit 2 is cation exchange resin, the volume is 4.7L, the EBCT is 45min, and the group 2 ion exchange units are reserved. 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 is anion exchange resin, the volume is 42L, the EBCT is 30min, and 2 groups are reserved. Average water yield COD, TN, NH during pilot plant test 4 + N and TP concentrations were 25.8, 7.0, 0.5 and 0.2mg/L, respectively, conforming to the first class 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 to be 1.0:1.0:1.0 (FIG. 6). The supernatant from the magnesium ammonium phosphate crystallization reactor flows into the regeneration-liquid reserve tank 7 for the next cycle. 562.9g of magnesium ammonium phosphate was recovered daily during the pilot plant. The recovered magnesium ammonium phosphate meets the standards promulgated by the Shaoxing standards Association, T/SXAS 005-2020, and the details are shown in Table 2.
Table 2 index comparison of recovered magnesium ammonium phosphate and magnesium ammonium phosphate standard in sewage
Note that: based on the dried sample.
In addition, the specific embodiments described in the present specification may differ in terms of parts, shapes of components, names, and the like. All equivalent or simple changes of the structure, characteristics and principle according to the inventive concept are included in the protection scope of the present invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions in a similar manner without departing from the scope of the invention as defined in the accompanying claims.
Claims (8)
1. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment is characterized in that the magnesium ammonium phosphate precipitation recovery process is implemented by adopting a magnesium ammonium phosphate precipitation recovery device, the magnesium ammonium phosphate precipitation recovery device comprises a main flow sewage treatment pipeline and a side flow regeneration liquid pipeline, the main flow sewage treatment pipeline comprises an ammonium ion exchange unit (2), an anoxic/aerobic reactor (3) and a phosphorus ion exchange unit (4) which are sequentially connected, the side flow regeneration liquid pipeline comprises a regeneration liquid reserve tank (7) with a regeneration liquid inside, the regeneration liquid reserve tank (7) is sequentially connected with the ammonium ion exchange unit (2), a calcium recovery sedimentation tank (5), the phosphorus ion exchange unit (4) and the magnesium ammonium phosphate sedimentation tank (6) through pipelines, and a water outlet of the magnesium ammonium phosphate sedimentation tank (6) is also connected with the regeneration liquid reserve tank (7) in a return manner;
the main flow sewage treatment pipeline further comprises a sewage water inlet pump (11) and a water inlet pretreatment unit (1) which are sequentially connected at the front end of the ammonium ion exchange unit (2), and the water inlet pretreatment unit (1) adopts chemical strengthening primary treatment;
the sewage inlet pump (11) is also provided with a branch which is directly connected with the anoxic/aerobic reactor (3);
the magnesium ammonium phosphate precipitation recovery process comprises the following steps:
s1, sending a part of sewage to be treated into an ammonium ion exchange unit (2), and rapidly capturing ammonia nitrogen in the sewage by an ammonium ion exchanger;
s2, the sewage treated by the ammonium ion exchange unit (2) and the other part of sewage to be treated are converged into the anoxic/aerobic bioreactor (3);
s3, after the sewage is treated by the anoxic/aerobic bioreactor (3), the sewage enters the phosphorus ion exchange unit (4), and the phosphorus ion exchanger rapidly captures phosphorus in the sewage to obtain purified sewage and discharges the purified sewage;
s4, stopping feeding the sewage to be treated after the set ion exchange time is reached, and evacuating the ammonium ion exchange unit (2) and the phosphorus ion exchange unit (4) for regeneration;
s5, during regeneration, the regeneration liquid in the regeneration liquid reserve tank (7) is sent into the ammonium ion exchange unit (2) to complete the regeneration of the ammonium ion exchanger, then the regeneration liquid enters the calcium recovery sedimentation tank (5), and the calcium recovery sedimentation agent is added into the calcium recovery sedimentation tank (5) and stirred, and is settled after full reaction;
s6, discharging water from the upper part of the calcium recovery sedimentation tank (5) into a phosphorus ion exchange unit (4), finishing the regeneration of the phosphorus ion exchanger, then flowing into a 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 to obtain precipitate, namely magnesium ammonium phosphate and recycling.
2. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment according to claim 1, wherein 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 in return connection with the anoxic tank (20), and the aerobic tank (21) is provided with a mixed liquor return pipe and is in return connection with the anoxic tank (20).
3. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment according to claim 1, wherein an ammonium ion exchange water inlet valve (13) and an ammonium ion exchange water outlet valve (14) are respectively arranged at the front end and the rear end of the ammonium ion exchange unit (2);
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).
4. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment according to claim 1, wherein the ammonium ion exchange unit (2) works in an up-flow or down-flow mode;
the phosphorus ion exchange unit (4) works in an up-flow or down-flow mode.
5. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment according to claim 1, wherein a regeneration liquid water inlet pump (12) and a regeneration liquid water inlet valve (15) are further arranged between the regeneration liquid reserve tank (7) and the ammonium ion exchange unit (2);
a regeneration liquid 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).
6. The magnesium ammonium phosphate precipitation recovery process based on ion exchange separation enrichment according to claim 1, wherein a phosphorus ion exchange regeneration liquid outlet valve (19) is further arranged on the phosphorus ion exchange unit (4), and a pH adjusting box (9) and a magnesium source doser (10) are further arranged on the magnesium ammonium phosphate precipitation tank (6).
7. The ion exchange separation and enrichment-based magnesium ammonium phosphate precipitation recovery process according to claim 1, wherein in the step S1, the flow rate ratio of the sewage to be treated is determined according to the mole ratio of nitrogen and phosphorus concentrations in the sewage;
in the step S1, the ammonium ion exchanger is selected from one or more of natural zeolite, modified zeolite, molecular sieve, vermiculite, montmorillonite and ion exchange resin;
in the step S1, the residence time of the sewage to be treated in the empty column of the ammonium ion exchange unit (2) is 1-300 min;
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 d;
in the step S2, the hydraulic retention time of the anoxic/aerobic bioreactor (3) is 0.5-48 h;
in the step S2, the phosphorus ion exchanger is selected from one or more of active carbon, metal oxide, ion exchange resin, molecular sieve and zeolite;
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.
8. The ion exchange separation enriched magnesium ammonium phosphate precipitation recovery process according to claim 1, wherein in step S5, the regeneration liquid comprises sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate solution or a mixture thereof;
in the step S5, the concentration of the regeneration liquid is 0.01-200 g/L;
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 on the ammonium ion exchanger is 0.1-72 h;
in step S5, the calcium recovery precipitant is selected from one or more of carbonate, bicarbonate, polyphosphate fluoride;
in the step S5, the hydraulic retention time of the calcium recovery sedimentation tank (5) is 0.1-24 h;
in 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 regenerating solution on the phosphorus ion exchanger is 0.1-72 h;
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, and sulfuric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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