CN114314988A - Iron phosphate wastewater treatment and salt recovery system and method - Google Patents
Iron phosphate wastewater treatment and salt recovery system and method Download PDFInfo
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- CN114314988A CN114314988A CN202111682056.6A CN202111682056A CN114314988A CN 114314988 A CN114314988 A CN 114314988A CN 202111682056 A CN202111682056 A CN 202111682056A CN 114314988 A CN114314988 A CN 114314988A
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 139
- 150000003839 salts Chemical class 0.000 title claims abstract description 120
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004065 wastewater treatment Methods 0.000 title claims description 26
- 238000011084 recovery Methods 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 243
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 230
- 239000008237 rinsing water Substances 0.000 claims abstract description 83
- 239000012452 mother liquor Substances 0.000 claims abstract description 81
- 239000002351 wastewater Substances 0.000 claims abstract description 70
- 238000002425 crystallisation Methods 0.000 claims abstract description 69
- 230000008025 crystallization Effects 0.000 claims abstract description 69
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 63
- 238000000926 separation method Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 26
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 26
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 239000000498 cooling water Substances 0.000 claims abstract description 13
- 238000011001 backwashing Methods 0.000 claims description 35
- 239000010802 sludge Substances 0.000 claims description 33
- 239000000706 filtrate Substances 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 230000001376 precipitating effect Effects 0.000 claims description 25
- 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 18
- 239000003729 cation exchange resin Substances 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 15
- 230000008020 evaporation Effects 0.000 claims description 14
- 238000005262 decarbonization Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 239000003002 pH adjusting agent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- -1 manganese, alkaline earth metals Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000000909 electrodialysis Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical class C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009510 drug design Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a system and a method for treating iron phosphate wastewater and recovering salt. In the system, the ferric phosphate rinsing water treatment module comprises a rinsing water adjusting device, a first mixed precipitation device, a first multi-media filter and a first ultrafiltration device which are sequentially connected; the first mixed precipitation device is connected with a first plate-and-frame filter press; the first plate-and-frame filter press is connected with the first multi-media filter; the iron phosphate mother liquor treatment module comprises a mother liquor adjusting device, a reaction device, a second multi-media filter and a second ultrafiltration device which are connected in sequence, and the first ultrafiltration device and the second ultrafiltration device are connected with the reverse osmosis module; the evaporative crystallization salt separation module comprises an evaporative crystallization salt separation system, a liquid inlet, a salt outlet and a cooling water outlet are arranged on the evaporative crystallization salt separation system, the reverse osmosis module is connected with the liquid inlet, and the cooling water outlet is also connected with the reverse osmosis module. After the treatment of the system, the final reuse water can be used as rinsing water for reuse, and the crystal salt can be recovered, thereby achieving the purpose of zero emission.
Description
Technical Field
The invention particularly relates to a system and a method for treating iron phosphate wastewater and recovering salt.
Background
With the market demand of lithium iron phosphate batteries in China greatly increasing, the demand of the iron phosphate as an ideal precursor of the lithium iron phosphate battery positive electrode material is increasing day by day, the process for producing the iron phosphate material is more and more advanced, and the process for producing the iron phosphate by the ammonia method is gradually the mainstream at present. When the iron phosphate is synthesized by an ammonia method, a large amount of wastewater is generated, and due to the influence of the process and raw materials, the main components in the wastewater contain high-concentration heavy metals such as nitrogen, phosphorus, fluorine, iron and manganese, alkaline earth metals such as magnesium, a small amount of other heavy metals such as nickel, cobalt and zinc, and partial fluoride ions, so that the treatment difficulty is high, the treatment method is improper, the environment is greatly influenced, the service life of production equipment is influenced, the operation cost is increased, and the development of enterprises is even restricted.
The scheme for treating iron phosphate wastewater in the prior art mainly comprises the following steps: the lime precipitation method is characterized in that phosphate radicals in the iron phosphate wastewater are precipitated by adding lime, but ammonia nitrogen cannot be removed by the lime precipitation method, measures for removing ammonia nitrogen are required to be added, a large amount of sludge is generated, the total salt in the wastewater exceeds the standard, and the environmental protection requirement cannot be met; the magnesium ammonium phosphate method (such as CN104609630B) simultaneously treats mother liquor and rinsing water (the two waste waters have different compositions and cause resource waste) by adding MgO and NaOH, removes total phosphorus and ammonia nitrogen, then concentrates the waste water and sends the concentrated waste water to an evaporative crystallization device, and sends waste salt out, wherein the waste salt in the method needs to be sent out for treatment, and the operation cost is high.
The scheme adopted in the prior art CN105000744B is as follows: adding ammonia, tubular microfiltration, primary RO, secondary RO, concentrated water RO and evaporative crystallization, wherein the concentrated water RO and the mother liquor are subjected to evaporative crystallization together, and the concentration rate of Reverse Osmosis (RO) is insufficient, so that the energy consumption is high; the pH is adjusted to 3.6-6, and only part of heavy metals and hardness ions can be removed; the mother liquor is not pretreated in the early stage, a large amount of heavy metal ions, calcium, magnesium and fluorine ions exist, and the evaporation, crystallization and scaling tendency is very serious; there is no exhaust gas absorption measure.
The adopted scheme in the prior art CN104609631B is as follows: the pretreatment system (PT), the reverse osmosis treatment system (RO) and the evaporation crystallization treatment system (VC) aim at wastewater which is 'produced water after nitrogen and phosphorus recovery treatment of a wastewater treatment station'.
The adopted scheme in the prior art CN204939035U is as follows: the method comprises the following steps of (1) performing primary reverse osmosis on iron phosphate wastewater in a regulating tank, performing reverse osmosis on primary reverse osmosis concentrated water, performing secondary reverse osmosis on primary reverse osmosis produced water and concentrated water reverse osmosis concentrated water, recycling secondary reverse osmosis produced water, and using the concentrated water reverse osmosis concentrated water as a raw material for producing a compound fertilizer or feeding the concentrated water into an evaporation crystallization device to produce mixed salt; wherein, the rinsing water and the mother liquor are mixed for treatment and directly adjusted to enter the reverse osmosis, and the requirement on the reverse osmosis device is very high; there is no exhaust gas absorption measure.
The adopted scheme of the prior art CN204939147U is as follows: the method comprises the following steps of (1) regulating a pool, primary reverse osmosis and secondary reverse osmosis, recycling secondary reverse osmosis produced water, returning secondary reverse osmosis concentrated water to the regulating pool, feeding the primary reverse osmosis concentrated water into electrodialysis, returning electrodialysis produced water to the regulating pool, and removing the electrodialysis concentrated water to a fertilizer plant; wherein, the rinsing water and the mother liquor are mixed for treatment and directly adjusted to enter the reverse osmosis, and the requirement on the reverse osmosis device is very high; no waste gas absorption measures; and electrodialysis is adopted, so that the operation energy consumption is higher.
Prior art CN209602165U discloses a zero release processing apparatus of ferric phosphate waste water, and the adoption scheme is: the pretreatment system, the ultrafiltration system, the nanofiltration system and the reverse osmosis system. Wherein, the rinsing water and the mother solution are mixed for treatment, which wastes resources; the pretreatment only removes iron, and lacks measures for removing other heavy metals, hardness ions and fluorine ions and removing partial organic matters; the concentrated water is directly recovered by phosphoric acid, and the waste water after evaporation and concentration still needs to be discharged.
Based on the state of the art, it was found that,
mixing rinsing water and mother liquor in the ferric phosphate wastewater: the ferric phosphate wastewater mainly comprises a mother solution and rinsing water, wherein the concentration of the former is higher than that of the latter: TDS (total salt content) of rinsing water before treatment is 4500-31000-N (ammonia nitrogen) 4000mg/L, TP (total phosphorus) 200-1500mg/L, pH2.3-2.6, mother liquor TDS (total salt content) 40000-60000mg/L, NH before treatment38000mg/L of N (ammonia nitrogen) 4000-8000mg/L, TP (total phosphorus) 2000-8000mg/L, pH1.6-2.0; the two streams of water are directly introduced into the reverse osmosis system, so that equipment and energy consumption are wasted (the low-concentration rinsing water dilutes the high-concentration mother liquor and then is concentrated through the RO system, so that a repeated process exists).
Secondly, the ferric phosphate wastewater treatment system in the prior art does not completely realize zero discharge, or the treated wastewater is the wastewater pretreated by a manufacturer, or the treatment is finished only after salt concentration, the concentrated wastewater is still discharged, or ammonia, nitrogen, phosphorus, metal ions and the like cannot be effectively removed, or the regulated wastewater directly enters a reverse osmosis device and an ultrafiltration device, so that the load on the precise filtration devices is large, and the operation cost and the treatment process are additionally increased.
Therefore, a system and a method for treating iron phosphate wastewater are urgently needed, not only can rinse water and mother liquor be separated and effectively treated, but also complete circulation in the system can be realized, zero discharge (water recycling and salt recovery) in the true sense is realized, relevant ions are removed, and long-term stable operation of equipment is ensured, so that the development of the iron phosphate lithium battery industry is promoted.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the rinsing water and the mother liquor in the ferric phosphate wastewater are mixed to cause resource waste, and a complete circulation loop cannot be formed in a ferric phosphate wastewater treatment system, so that the zero discharge cannot be realized in the true sense, and provides a ferric phosphate wastewater treatment and salt recovery system and a method thereof.
The invention solves the technical problems through the following technical scheme:
the invention provides a system for treating iron phosphate wastewater and recovering salt, which comprises an iron phosphate rinsing water treatment module, an iron phosphate mother liquor treatment module, a reverse osmosis module and an evaporative crystallization salt separation module; the ferric phosphate rinsing water treatment module and the ferric phosphate mother liquor treatment module are independently connected with the reverse osmosis module, and a concentrated water pipeline of the reverse osmosis module is connected with the evaporative crystallization salt separation module;
the iron phosphate rinsing water treatment module comprises a rinsing water adjusting device, a first mixed precipitation device, a first multi-media filter and a first ultrafiltration device which are sequentially connected along the flow direction of iron phosphate rinsing water; a rinsing water inlet is formed in the rinsing water adjusting device, and a first pH adjusting agent inlet is formed in the first mixed precipitation device; the first mixed precipitation device is connected with a first plate-and-frame filter press through a sludge pipeline; a filtrate pipeline of the first plate-and-frame filter press is connected with the first multi-media filter, and a first sludge outlet is formed in the first plate-and-frame filter press;
the iron phosphate mother liquor treatment module comprises a mother liquor adjusting device, a reaction device, a second multi-media filter and a second ultrafiltration device which are sequentially connected along the flowing direction of the iron phosphate mother liquor, wherein a mother liquor inlet is formed in the mother liquor adjusting device, and a second pH regulator inlet and a reflux inlet are formed in the reaction device;
the reverse osmosis module is provided with a water producing port for extracting reuse water;
the iron phosphate rinsing water treatment module and the iron phosphate mother liquor treatment module are respectively connected with the reverse osmosis module through a filtrate pipeline of the first ultrafiltration device and a filtrate pipeline of the second ultrafiltration device;
the evaporative crystallization salt separation module comprises an evaporative crystallization salt separation system, wherein a liquid inlet, a salt outlet and a cooling water outlet are arranged on the evaporative crystallization salt separation system, a concentrated water pipeline of the reverse osmosis module is connected with the liquid inlet, and the cooling water outlet is also connected with the reverse osmosis module.
Alternatively, the concentrated water pipeline of the reverse osmosis module is also provided with a concentrated water pipeline which flows back to the first ultrafiltration device besides being connected with the liquid inlet of the evaporative crystallization salt separation system.
In the present invention, preferably, the iron phosphate rinsing water treatment module further includes a cation exchange resin column, and the first ultrafiltration device is connected to the reverse osmosis module through the cation exchange resin column.
In the present invention, preferably, the iron phosphate rinsing water treatment module further includes a decarbonization device, and the first ultrafiltration device is connected to the reverse osmosis module through the decarbonization device.
Preferably, the iron phosphate rinsing water treatment module further comprises a cation exchange resin column and a decarbonization device, and the first ultrafiltration device, the cation exchange resin column, the decarbonization device and the reverse osmosis module are sequentially connected. Cation exchange resin and other processes, effectively solves the harm of impurity ion enrichment to a reverse osmosis system and an evaporative crystallization system in the concentration process.
In the present invention, preferably, the first multimedia filter and the first ultrafiltration device are both provided with a first backwashing water inlet and a first backwashing water outlet, and the first backwashing water outlet is connected to the water inlet of the first mixed precipitation device.
Preferably, the iron phosphate rinsing water treatment module further comprises a first water filtering device, and the first mixing and precipitating device and the first plate-and-frame filter press are both communicated with the first multimedia filter through the first water filtering device. The first water filtering device is preferably further provided with a first backwashing water outlet, and the first backwashing water outlet is connected with the first backwashing water inlet.
In the present invention, preferably, a mother liquor heat exchanger is disposed between the mother liquor adjusting device and the reaction device.
In the present invention, preferably, the iron phosphate mother liquor treatment module further comprises a second plate-and-frame filter press, a third plate-and-frame filter press and a second mixing and precipitating device;
the reaction device, the second plate-and-frame filter press, the second mixed precipitation device and the second multi-media filter are sequentially connected along the flowing direction of the ferric phosphate mother liquor;
and a second sludge outlet is formed in the second plate-and-frame filter press and used for outputting sludge. And a third pH regulator inlet is formed in the second mixed precipitation device, and a sludge pipeline of the second mixed precipitation device is connected with a third plate-and-frame filter press. And a filtrate pipeline of the third plate-and-frame filter press is connected with a reflux inlet of the reaction device, and a third sludge outlet is formed in the third plate-and-frame filter press and used for outputting sludge.
In the present invention, preferably, a second backwashing water inlet and a second backwashing water outlet are provided on the second multimedia filter and the second ultrafiltration device, and the second backwashing water outlet is connected to the reflux liquid inlet of the reaction device.
Preferably, a second water filtering device is further arranged on a filtrate pipeline of the second ultrafiltration device, and a water outlet of the second water filtering device is connected with the reverse osmosis module. Preferably, the second water filtering device is further provided with a second backwashing water outlet, and the second backwashing water outlet is connected with the second backwashing water inlet.
In the present invention, the reaction apparatus is preferably further provided with a fourth sludge outlet for discharging sludge.
In the present invention, preferably, the reverse osmosis module includes a wastewater reverse osmosis module and a concentrated water reverse osmosis module. And the iron phosphate rinsing water treatment module is connected with a liquid inlet of the wastewater reverse osmosis module through a filtrate pipeline of the first ultrafiltration device. And the iron phosphate mother liquor treatment module is connected with a liquid inlet of the concentrated water reverse osmosis module through a filtrate pipeline of the second ultrafiltration device. And a concentrated water pipeline of the wastewater reverse osmosis module is connected with a liquid inlet of the concentrated water reverse osmosis module.
The water producing port is arranged on the wastewater reverse osmosis module.
The concentrated water pipeline of the concentrated water reverse osmosis module is connected with the liquid inlet of the evaporative crystallization salt separation system, and the water production pipeline of the concentrated water reverse osmosis module is connected with the wastewater reverse osmosis module.
And a cooling water outlet of the evaporation crystallization salt separation system is connected with the concentrated water reverse osmosis module.
Alternatively, the concentrated water pipeline of the concentrated water reverse osmosis module is also provided with a concentrated water pipeline which flows back to the first ultrafiltration device besides being connected with the evaporative crystallization salt separation system.
Wherein, generally, the wastewater reverse osmosis module and/or the concentrated water reverse osmosis module comprise a plurality of single-stage reverse osmosis devices which are connected in series in sequence. Preferably, the number of the single-stage reverse osmosis devices is 1-3. In this case, the water producing port on the wastewater reverse osmosis module generally refers to a water producing port on the last single-stage reverse osmosis device; meanwhile, the concentrated water pipelines of the single-stage reverse osmosis devices in the wastewater reverse osmosis module are connected with the concentrated water reverse osmosis module. The water production pipeline of the concentrated water reverse osmosis module connected with the wastewater reverse osmosis module is also generally referred to as the water production pipeline of the last single-stage reverse osmosis device; meanwhile, the concentrated water pipelines of each single-stage reverse osmosis device in the concentrated water reverse osmosis module are generally connected with the evaporative crystallization salt separation system.
Wherein, more preferably, the waste water reverse osmosis module includes one-level reverse osmosis unit, second grade reverse osmosis unit and the terminal reverse osmosis unit that connect gradually through the product water pipeline. The iron phosphate rinsing water treatment module is connected with a liquid inlet of the primary reverse osmosis device through a filtrate pipeline of the first ultrafiltration device; and the water producing port is arranged on the terminal reverse osmosis device.
The concentrated water reverse osmosis module comprises a concentrated water first-stage reverse osmosis device, a concentrated water second-stage reverse osmosis device and a concentration reverse osmosis device.
The concentrated water pipeline of the first-stage reverse osmosis device is connected with the concentrated water first-stage reverse osmosis device, and the concentrated water first-stage reverse osmosis device is sequentially connected with the concentrated water second-stage reverse osmosis device and the terminal reverse osmosis device through a water production pipeline.
And a concentrated water pipeline of the second-stage reverse osmosis device is connected with the concentrated water second-stage reverse osmosis device.
The concentrated water pipeline of the concentrated water first-stage reverse osmosis device is connected with the concentrated reverse osmosis device, and the concentrated water pipeline of the concentrated reverse osmosis device is connected with the liquid inlet of the evaporation crystallization salt separation system, the water production pipeline of the concentrated reverse osmosis device and the cooling water outlet of the evaporation crystallization salt separation system are connected with the concentrated water second-stage reverse osmosis device.
In this preferred embodiment, the concentrate line of the concentrate secondary reverse osmosis device is connected to the inlet of the first ultrafiltration device, in addition to the concentrate line of the concentrate reverse osmosis device being connected to the evaporative crystallization salt separation system.
Wherein, preferably, the concentrated water pipeline of the terminal reverse osmosis device is connected with the concentrated water secondary reverse osmosis device.
In the invention, the mother liquor and the rinse water are separately treated and enter the reverse osmosis module when the TDS of the mother liquor and the TDS of the rinse water are close to each other, thereby ensuring the reasonable design of the system, avoiding the repetition of dilution and concentration and effectively reducing the equipment scale and the operation energy consumption of the system.
In the present invention, the evaporative crystallization salt separation system can be a device for evaporative crystallization salt separation conventional in the art, such as an FC type crystallizer and a continuous flash evaporation crystallization system which are connected in series in sequence.
In the present invention, the first multimedia filter and/or the second multimedia filter may be conventional in the art, for example, the filter material is quartz sand and activated carbon, or quartz sand and activated anthracite. Which can remove part of organic matter and suspended matter.
According to the invention, water can be supplemented to the system as required to supplement water brought out by the system due to natural evaporation, sludge and crystallized salt.
The invention also provides a method for treating the iron phosphate wastewater and recovering salt, which adopts the iron phosphate wastewater treatment and salt recovery system for treatment and comprises the following steps: inputting rinsing water in the iron phosphate wastewater to be treated from a rinsing water inlet on the rinsing water regulating device, and inputting mother liquor in the iron phosphate wastewater to be treated from a mother liquor inlet on the mother liquor regulating device; adjusting the pH value in the first mixing and precipitating device to 8-9.5, and adjusting the pH value in the reaction device to 5-6.5; and recovering the reuse water from the water production port of the reverse osmosis module, and outputting the salt from the salt outlet of the evaporative crystallization salt separation system.
In the invention, preferably, when the iron phosphate wastewater treatment and salt recovery system comprises a second mixing and precipitating device, the pH in the second mixing and precipitating device needs to be adjusted to 8-9.5.
In the present invention, the manner of adjusting the pH may be conventional in the art, and for example, the pH adjustment is performed using aqueous ammonia.
In the present invention, hardness ions such as heavy metals and calcium and magnesium, and partial fluorine removal can be performed by adjusting the pH.
In the present invention, when the iron phosphate wastewater treatment and salt recovery system includes a cation exchange resin column, the cation exchange resin column is preferably a weak acid cation bed.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
after passing through the iron phosphate wastewater treatment system, the TDS (total salt content) in the reuse water is less than 10mg/L, NH3N (ammonia nitrogen) < 5mg/L, TP (total phosphorus) < 0.5mg/L, pH 5.5.5-7.5, system TDS (total salt content), NH3The average removal rate of N (ammonia nitrogen) and TP (total phosphorus) is more than 99.8 percent. The method solves the pollution problem of the new energy iron phosphate wastewater, the final reuse water can be reused as rinsing water in the iron phosphate production process, evaporative crystallization salt separation treatment is carried out through an evaporative crystallization salt separation system to obtain high-quality ammonium sulfate and ammonium dihydrogen phosphate, and the condensate water is reused and treated to achieve the purpose of zero discharge.
After the iron phosphate wastewater treatment system of this application, get rid of heavy metal basically, mud can regard as chemical fertilizer raw materials, avoids the useless emission of danger.
After the ferric phosphate wastewater treatment system of this application, impurity obtains better getting rid of in the strong brine, can ensure that follow-up salt crystal system that divides separates out the crystal salt of high-quality.
Drawings
Fig. 1 is a system for treating iron phosphate wastewater and recovering salts according to example 1 of the present invention.
Fig. 2 is a system for treating iron phosphate wastewater and recovering salts according to example 2 of the present invention.
Fig. 3 is a system for treating iron phosphate wastewater and recovering salts according to example 3 of the present invention.
Description of the reference numerals
Iron phosphate rinsing water treatment module 1
Rinsing water adjusting device 101
First mixing and precipitating device 102
First plate and frame filter press 105
First pH adjuster inlet 106
First water filtering means 107
Cation exchange resin column 108
Ferric phosphate mother liquor processing module 2
Mother liquor adjusting device 201
Second pH adjustor inlet 205
Mother liquor heat exchanger 206
Second water filtering device 207
The third plate frame filter press 208
Second mixing and precipitating device 209
Second plate and frame filter press 210
Third pH adjustor inlet 211
Wastewater reverse osmosis module 31
Concentrated water reverse osmosis module 32
Concentrated water second-stage reverse osmosis device 301
Concentration reverse osmosis device 302
First-stage reverse osmosis device 303
Two-stage reverse osmosis unit 304
Terminal reverse osmosis unit 305
Concentrated water first-stage reverse osmosis device 306
Evaporative crystallization salt separation module 4
And (4) evaporating, crystallizing and separating salt system 41.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The system for treating the iron phosphate wastewater and recovering the salt comprises an iron phosphate rinsing water treatment module 1, an iron phosphate mother liquor treatment module 2, a reverse osmosis module 3 and an evaporative crystallization salt separation module 4, wherein the iron phosphate rinsing water treatment module 1 is connected with the iron phosphate mother liquor treatment module; the ferric phosphate rinsing water treatment module 1 and the ferric phosphate mother liquor treatment module 2 are independently connected with a reverse osmosis module 3, and the reverse osmosis module 3 is connected with an evaporative crystallization salt separation module 4;
the iron phosphate rinsing water treatment module 1 comprises a rinsing water adjusting device 101, a first mixing and precipitating device 102, a first multi-media filter 103 and a first ultrafiltration device 104 which are sequentially connected along the flow direction of iron phosphate rinsing water; a rinsing water inlet is arranged on the rinsing water adjusting device 101, and a first pH adjusting agent inlet 106 is arranged on the first mixed precipitation device 102; the first mixing and precipitating device 102 is connected with a first plate-and-frame filter press 105 through a sludge pipeline; a filtrate pipeline of the first plate-and-frame filter press 105 is connected with the first multimedia filter 103, and a first sludge outlet is arranged on the first plate-and-frame filter press 105;
the iron phosphate mother liquor treatment module 2 comprises a mother liquor adjusting device 201, a reaction device 202, a second multi-media filter 203 and a second ultrafiltration device 204 which are sequentially connected along the flow direction of the iron phosphate mother liquor, wherein a mother liquor inlet is formed in the mother liquor adjusting device 201, and a second pH regulator inlet 205 and a reflux liquid inlet (not shown in the figure) are formed in the reaction device 202;
the reverse osmosis module 3 is provided with a water producing port for extracting reuse water;
the iron phosphate rinsing water treatment module 1 and the iron phosphate mother liquor treatment module 2 are respectively connected with the reverse osmosis module 3 through a filtrate pipeline of the first ultrafiltration device 104 and a filtrate pipeline of the second ultrafiltration device 204;
the evaporative crystallization salt separation module 4 comprises an evaporative crystallization salt separation system 41, a liquid inlet, a salt outlet and a cooling water outlet are arranged on the evaporative crystallization salt separation system 41, one strand of a concentrated water pipeline of the reverse osmosis module 3 is connected with the liquid inlet, the other strand of the concentrated water pipeline is connected with the first ultrafiltration device 104, the cooling water outlet is connected with the reverse osmosis module 3, and the salt outlet is used for outputting salt.
Example 2
The iron phosphate wastewater treatment and salt recovery system shown in figure 2,
the system comprises an iron phosphate rinsing water treatment module 1, an iron phosphate mother liquor treatment module 2, a reverse osmosis module 3 and an evaporative crystallization salt separation module 4; the ferric phosphate rinsing water treatment module 1 and the ferric phosphate mother liquor treatment module 2 are independently connected with a reverse osmosis module 3, and the reverse osmosis module 3 is connected with an evaporative crystallization salt separation module 4;
the iron phosphate rinsing water treatment module 1 comprises a rinsing water adjusting device 101, a first mixing and precipitating device 102, a first multi-media filter 103 and a first ultrafiltration device 104 which are sequentially connected along the flow direction of iron phosphate rinsing water; a rinsing water inlet is arranged on the rinsing water adjusting device 101, and a first pH adjusting agent inlet 106 is arranged on the first mixed precipitation device 102; the first mixing and precipitating device 102 is connected with a first plate-and-frame filter press 105 through a sludge pipeline; a filtrate pipeline of the first plate-and-frame filter press 105 is connected with the first multimedia filter 103, and a first sludge outlet is arranged on the first plate-and-frame filter press 105;
the iron phosphate mother liquor treatment module 2 comprises a mother liquor adjusting device 201, a reaction device 202, a second multi-media filter 203 and a second ultrafiltration device 204 which are sequentially connected along the flow direction of the iron phosphate mother liquor, wherein a mother liquor inlet is formed in the mother liquor adjusting device 201, and a second pH regulator inlet 205 is formed in the reaction device 202;
the evaporative crystallization salt separation module 4 comprises an evaporative crystallization salt separation system 41, and the evaporative crystallization salt separation system 41 is further provided with a salt outlet for outputting salt.
In this embodiment, the reverse osmosis module 3 includes a wastewater reverse osmosis module 31 and a concentrated water reverse osmosis module 32; the ferric phosphate rinsing water treatment module 1 is connected with a liquid inlet of the wastewater reverse osmosis module 31 through a filtrate pipeline of the first ultrafiltration device 104; the ferric phosphate mother liquor treatment module 2 is connected with a liquid inlet of the concentrated water reverse osmosis module 32 through a filtrate pipeline of the second ultrafiltration device 204; a concentrated water pipeline of the wastewater reverse osmosis module 31 is connected with a liquid inlet of the concentrated water reverse osmosis module 32; the water producing port is arranged on the wastewater reverse osmosis module 31; one strand of the concentrated water pipeline of the concentrated water reverse osmosis module 32 is connected with the evaporative crystallization salt separation system 41, the other strand of the concentrated water pipeline is connected with the first ultrafiltration device 104, and the water production pipeline of the concentrated water reverse osmosis module 32 is connected with the wastewater reverse osmosis module 31; the cooling water pipeline of the evaporative crystallization salt separation system 41 is connected with the concentrated water reverse osmosis module 32.
In this embodiment, the iron phosphate rinsing water treatment module 1 includes a cation exchange resin column 108 and a decarbonization device 109, and the first ultrafiltration device 104, the cation exchange resin column 108, and the decarbonization device 109 are connected to the wastewater reverse osmosis module 31 in sequence. Cation exchange resin (weak acid cation bed in this embodiment) and other processes, effectively solves the harm of impurity ion enrichment to reverse osmosis system and evaporative crystallization system in the concentration process.
In this embodiment, the first multimedia filter 103 and the first ultrafiltration device 104 are both provided with a first backwash water inlet and a first backwash water outlet, and the first backwash water outlet is connected with the water inlet of the first mixed precipitation device 102.
In this embodiment, the ferric phosphate rinse water treatment module 1 further comprises a first water filtering device 107, and the first mixing and precipitating device 102 and the first plate-and-frame filter press 105 are both communicated with the first multimedia filter 103 through the first water filtering device 107. The first water filtering device 107 is further provided with a first backwashing water outlet, and the first backwashing water outlet is connected with the first backwashing water inlet.
In this embodiment, a mother liquid heat exchanger 206 is disposed between the mother liquid adjusting device 201 and the reaction device 202.
In this embodiment, the second multimedia filter 203 and the second ultrafiltration device 204 are both provided with a second backwash water inlet and a second backwash water outlet, and the second backwash water outlet is connected with the reflux inlet of the reaction device 202.
In this embodiment, a second water filtering device 207 is further disposed on a filtrate pipeline of the second ultrafiltration device 204, and a water outlet of the second water filtering device 207 is connected to the reverse osmosis module 3. The second water filtering device 207 is further provided with a second backwashing water outlet, and the second backwashing water outlet is connected with the second backwashing water inlet.
In this embodiment, the reaction device 202 is further provided with a fourth sludge outlet for discharging sludge.
In this embodiment, the wastewater reverse osmosis module 31 and the concentrated water reverse osmosis module 32 each include 2 single-stage reverse osmosis devices (not shown) connected in series. In this case, the water producing port on the wastewater reverse osmosis module 31 generally refers to the water producing port on the last single-stage reverse osmosis device; meanwhile, the concentrated water pipeline of each single-stage reverse osmosis device in the wastewater reverse osmosis module 31 is connected with the concentrated water reverse osmosis module 32. The product water line of the concentrate reverse osmosis module 32 connected to the waste water reverse osmosis module 31 is also generally referred to as the product water line of the last single-stage reverse osmosis unit.
In this embodiment, separately handle mother liquor, rinsing water, get into reverse osmosis module 3 when TDS between them is close, ensured the rational design of system, avoid diluting, concentrated repetition, effectively reduce system equipment scale, operation energy consumption.
In this embodiment, the evaporative crystallization salt separation system 41 is connected in series with an FC type crystallizer and a continuous flash evaporation crystallization system (not shown) in the conventional manner in the field.
Example 3
The iron phosphate wastewater treatment and salt recovery system shown in figure 3,
the system comprises an iron phosphate rinsing water treatment module 1, an iron phosphate mother liquor treatment module 2, a reverse osmosis module 3 and an evaporative crystallization salt separation module 4; the ferric phosphate rinsing water treatment module 1 and the ferric phosphate mother liquor treatment module 2 are independently connected with a reverse osmosis module 3, and the reverse osmosis module 3 is connected with an evaporative crystallization salt separation module 4; the concentrated water pipeline of the reverse osmosis module 3 is connected with the liquid inlet of the evaporative crystallization salt separation system 41 and is also provided with a concentrated water pipeline which flows back to the first ultrafiltration device 104;
the iron phosphate rinsing water treatment module 1 comprises a rinsing water adjusting device 101, a first mixing and precipitating device 102, a first multi-media filter 103 and a first ultrafiltration device 104 which are sequentially connected along the flow direction of iron phosphate rinsing water; a rinsing water inlet is arranged on the rinsing water adjusting device 101, and a first pH adjusting agent inlet 106 is arranged on the first mixed precipitation device 102; the first mixing and precipitating device 102 is connected with a first plate-and-frame filter press 105 through a sludge pipeline; a filtrate pipeline of the first plate-and-frame filter press 105 is connected with the first multimedia filter 103, and a first sludge outlet is arranged on the first plate-and-frame filter press 105;
the iron phosphate mother liquor treatment module 2 comprises a mother liquor adjusting device 201, a reaction device 202, a second multi-media filter 203 and a second ultrafiltration device 204 which are sequentially connected along the flow direction of the iron phosphate mother liquor, wherein a mother liquor inlet is formed in the mother liquor adjusting device 201, and a second pH regulator inlet 205 and a reflux liquid inlet are formed in the reaction device 202;
the evaporative crystallization salt separation module 4 comprises an evaporative crystallization salt separation system 41, and the evaporative crystallization salt separation system 41 is further provided with a salt outlet for outputting salt.
In this embodiment, the reverse osmosis module 3 includes a wastewater reverse osmosis module 31 and a concentrated water reverse osmosis module 32; the wastewater reverse osmosis module 31 comprises a primary reverse osmosis device 303, a secondary reverse osmosis device 304 and a terminal reverse osmosis device 305 which are sequentially connected through a water production pipeline; the iron phosphate rinsing water treatment module 1 is connected with a liquid inlet of the primary reverse osmosis device 303 through a filtrate pipeline of the first ultrafiltration device 104; and the water producing port is arranged on the terminal reverse osmosis device 305; the concentrated water reverse osmosis module 32 comprises a concentrated water first-stage reverse osmosis device 306, a concentrated water second-stage reverse osmosis device 301 and a concentration reverse osmosis device 302; a concentrated water pipeline of the first-stage reverse osmosis device 303 is connected with a concentrated water first-stage reverse osmosis device 306, and the concentrated water first-stage reverse osmosis device 306 is sequentially connected with a concentrated water second-stage reverse osmosis device 301 and a terminal reverse osmosis device 305 through a water production pipeline; a concentrated water pipeline of the second-stage reverse osmosis device 304 is connected with the concentrated water second-stage reverse osmosis device 301; a concentrated water pipeline of the concentrated water first-stage reverse osmosis device 306 is connected with the concentrated reverse osmosis device 302, a concentrated water pipeline of the concentrated reverse osmosis device 302 is connected with a liquid inlet of the evaporative crystallization salt separation system 41, a water production pipeline of the concentrated reverse osmosis device 302 and a cooling water outlet of the evaporative crystallization salt separation system 41 are connected with the concentrated water second-stage reverse osmosis device 301.
In this embodiment, in addition to the connection of the concentrate line of the concentration reverse osmosis device 302 to the evaporative crystallization salt separation system 41, the concentrate line of the concentrate secondary reverse osmosis device 301 is also connected to the inlet of the first ultrafiltration device 104.
In this embodiment, the iron phosphate rinsing water treatment module 1 includes a cation exchange resin column 108 and a decarbonization device 109, and the first ultrafiltration device 104, the cation exchange resin column 108, and the decarbonization device 109 are connected to the wastewater reverse osmosis module 31 in sequence. Cation exchange resin (weak acid cation bed in this embodiment) and other processes, effectively solves the harm of impurity ion enrichment to reverse osmosis system and evaporative crystallization system in the concentration process.
In this embodiment, the first multimedia filter 103 and the first ultrafiltration device 104 are both provided with a first backwash water inlet and a first backwash water outlet, and the first backwash water outlet is connected with the water inlet of the first mixed precipitation device 102.
In this embodiment, the ferric phosphate rinse water treatment module 1 further comprises a first water filtering device 107, and the first mixing and precipitating device 102 and the first plate-and-frame filter press 105 are both communicated with the first multimedia filter 103 through the first water filtering device 107. The first water filtering device 107 is further provided with a first backwashing water outlet, and the first backwashing water outlet is connected with the first backwashing water inlet.
In this embodiment, a mother liquid heat exchanger 206 is disposed between the mother liquid adjusting device 201 and the reaction device 202.
In this embodiment, the iron phosphate mother liquor processing module 2 further includes a second plate-and-frame filter press 210, a third plate-and-frame filter press 208, and a second mixing and precipitating device 209; the reaction device 202, the second plate-and-frame filter press 210, the second mixing and precipitating device 209 and the second multimedia filter 203 are sequentially connected along the flow direction of the iron phosphate mother liquor; the second plate-and-frame filter press 210 is provided with a second sludge outlet for outputting sludge; a third pH regulator inlet 211 is arranged on the second mixing and precipitating device 209, and a sludge pipeline of the second mixing and precipitating device 209 is connected with a third plate and frame filter press 208; a filtrate pipeline of the third plate-and-frame filter press 208 is connected with a reflux inlet of the reaction device 202, and a third sludge outlet is arranged on the third plate-and-frame filter press 208 and used for outputting sludge.
In this embodiment, the second multimedia filter 203 and the second ultrafiltration device 204 are both provided with a second backwash water inlet and a second backwash water outlet, and the second backwash water outlet is connected with the reflux inlet of the reaction device 202.
In this embodiment, a second water filtering device 207 is further disposed on a filtrate pipeline of the second ultrafiltration device 204, and a water outlet of the second water filtering device 207 is connected to the reverse osmosis module 3. The second water filtering device 207 is further provided with a second backwashing water outlet, and the second backwashing water outlet is connected with the second backwashing water inlet.
In this embodiment, the reaction device 202 is further provided with a fourth sludge outlet for discharging sludge.
In this embodiment, separately handle mother liquor, rinsing water, get into reverse osmosis module 3 when TDS between them is close, ensured the rational design of system, avoid diluting, concentrated repetition, effectively reduce system equipment scale, operation energy consumption.
In this embodiment, the evaporative crystallization salt separation system 41 is connected in series with an FC type crystallizer and a continuous flash evaporation crystallization system (not shown) in the conventional manner in the field.
Example 4
The iron phosphate wastewater treatment and salt recovery system in example 3 was used for treatment, and the wastewater used was 9840 tons/day (410 m) of iron phosphate project supporting 4.7 ten thousand tons of iron phosphate produced annually by a new energy enterprise3And h) performing zero discharge project of iron phosphate wastewater treatment. The method specifically comprises the following steps:
inputting rinsing water in the iron phosphate wastewater to be treated from a rinsing water inlet on the rinsing water regulating device 101, and inputting mother liquor in the iron phosphate wastewater to be treated from a mother liquor inlet on the mother liquor regulating device 201; adjusting the pH value in the first mixing and precipitating device 102 to 8-9.5, and adjusting the pH value in the reaction device 202 to 5-6.5; the water producing port of the reverse osmosis module 3 is used for extracting the reuse water, and the salt is output from the salt outlet of the evaporative crystallization salt separating system 41.
In this embodiment, the pH adjustment mode is to adjust the pH by using ammonia water, and the ammonia water is added through the first pH adjuster inlet 106, the second pH adjuster inlet 205, and the third pH adjuster inlet 211 respectively to adjust; wherein the pH value in the second mixing and precipitating device 209 is adjusted to 8-9.5.
In this example, hardness ions such as heavy metals and calcium and magnesium, and partial fluorine removal can be performed by adjusting the pH.
In this embodiment, the filter materials of the first multimedia filter 103 and the second multimedia filter 203 are quartz sand and activated carbon, or quartz sand and activated anthracite, which can remove part of organic matters and suspended matters.
In this embodiment, the system may be replenished as needed to replenish water brought out by the system due to natural evaporation, sludge, and crystallized salts.
Wherein, the parameters of rinsing water and mother liquor in the iron phosphate wastewater to be treated are shown in the following table 1:
TABLE 1
Finally, the TDS (total salt content) in the reclaimed water is less than 10mg/L, NH3N (ammonia nitrogen) < 5mg/L, TP (total phosphorus) < 0.5mg/L, pH 5.5.5-7.5, system TDS (total salt content), NH3The average removal rate of N (ammonia nitrogen) and TP (total phosphorus) is more than 99.8 percent. The method solves the pollution problem of the new energy iron phosphate wastewater, the final reuse water can be reused as rinsing water in the iron phosphate production process, evaporative crystallization salt separation treatment is carried out through the evaporative crystallization salt separation system 41 to obtain high-quality ammonium sulfate and ammonium dihydrogen phosphate, and the condensate water is reused and treated to achieve the purpose of zero emission.
Claims (10)
1. A system for treating iron phosphate wastewater and recovering salt is characterized by comprising an iron phosphate rinsing water treatment module, an iron phosphate mother liquor treatment module, a reverse osmosis module and an evaporative crystallization salt separation module; the ferric phosphate rinsing water treatment module and the ferric phosphate mother liquor treatment module are independently connected with the reverse osmosis module, and a concentrated water pipeline of the reverse osmosis module is connected with the evaporative crystallization salt separation module;
the iron phosphate rinsing water treatment module comprises a rinsing water adjusting device, a first mixed precipitation device, a first multi-media filter and a first ultrafiltration device which are sequentially connected along the flow direction of iron phosphate rinsing water; a rinsing water inlet is formed in the rinsing water adjusting device, and a first pH adjusting agent inlet is formed in the first mixed precipitation device; the first mixed precipitation device is connected with a first plate-and-frame filter press through a sludge pipeline; a filtrate pipeline of the first plate-and-frame filter press is connected with the first multi-media filter, and a first sludge outlet is formed in the first plate-and-frame filter press;
the iron phosphate mother liquor treatment module comprises a mother liquor adjusting device, a reaction device, a second multi-media filter and a second ultrafiltration device which are sequentially connected along the flowing direction of the iron phosphate mother liquor, wherein a mother liquor inlet is formed in the mother liquor adjusting device, and a second pH regulator inlet and a reflux inlet are formed in the reaction device;
the reverse osmosis module is provided with a water producing port;
the iron phosphate rinsing water treatment module and the iron phosphate mother liquor treatment module are respectively connected with the reverse osmosis module through a filtrate pipeline of the first ultrafiltration device and a filtrate pipeline of the second ultrafiltration device;
the evaporative crystallization salt separation module comprises an evaporative crystallization salt separation system, wherein a liquid inlet, a salt outlet and a cooling water outlet are arranged on the evaporative crystallization salt separation system, a concentrated water pipeline of the reverse osmosis module is connected with the liquid inlet, and the cooling water outlet is also connected with the reverse osmosis module.
2. The iron phosphate wastewater treatment and salt recovery system according to claim 1,
the concentrated water pipeline of the reverse osmosis module is also provided with a concentrated water pipeline which flows back to the first ultrafiltration device.
3. The iron phosphate wastewater treatment and salt recovery system according to claim 1,
the iron phosphate rinsing water treatment module also comprises a cation exchange resin column, and the first ultrafiltration device is connected with the reverse osmosis module through the cation exchange resin column;
and/or the iron phosphate rinsing water treatment module further comprises a decarbonization device, and the first ultrafiltration device is connected with the reverse osmosis module through the decarbonization device;
preferably, the iron phosphate rinsing water treatment module further comprises a cation exchange resin column and a decarbonization device, and the first ultrafiltration device, the cation exchange resin column and the decarbonization device are sequentially connected with the reverse osmosis module;
and/or a first backwashing water inlet and a first backwashing water outlet are formed in the first multimedia filter and the first ultrafiltration device, and the first backwashing water outlet is connected with a water inlet of the first mixed precipitation device; preferably, the iron phosphate rinsing water treatment module further comprises a first water filtering device, and the first mixing and precipitating device and the first plate-and-frame filter press are both communicated with the first multimedia filter through the first water filtering device; the first water filtering device is preferably provided with a first backwashing water outlet which is connected with the first backwashing water inlet;
and/or a mother liquor heat exchanger is arranged between the mother liquor adjusting device and the reaction device.
4. The iron phosphate wastewater treatment and salt recovery system according to claim 1,
the iron phosphate mother liquor treatment module also comprises a second plate-and-frame filter press, a third plate-and-frame filter press and a second mixed precipitation device;
the reaction device, the second plate-and-frame filter press, the second mixed precipitation device and the second multi-media filter are sequentially connected along the flowing direction of the ferric phosphate mother liquor;
a second sludge outlet is formed in the second plate-and-frame filter press; a third pH regulator inlet is formed in the second mixed precipitation device, and a sludge pipeline of the second mixed precipitation device is connected with a third plate-and-frame filter press; and a filtrate pipeline of the third plate-and-frame filter press is connected with a reflux inlet of the reaction device, and a third sludge outlet is formed in the third plate-and-frame filter press.
5. The iron phosphate wastewater treatment and salt recovery system according to claim 1,
the reaction device is also provided with a fourth sludge outlet;
and/or a second backwashing water inlet and a second backwashing water outlet are formed in the second multimedia filter and the second ultrafiltration device, and the second backwashing water outlet is connected with a reflux liquid inlet of the reaction device;
preferably, a filtrate pipeline of the second ultrafiltration device is further provided with a second water filtering device, and a water outlet of the second water filtering device is connected with the reverse osmosis module; preferably, the second water filtering device is further provided with a second backwashing water outlet, and the second backwashing water outlet is connected with the second backwashing water inlet.
6. The iron phosphate wastewater treatment and salt recovery system of claim 1, wherein the reverse osmosis module comprises a wastewater reverse osmosis module and a concentrate reverse osmosis module; the iron phosphate rinsing water treatment module is connected with a liquid inlet of the wastewater reverse osmosis module through a filtrate pipeline of the first ultrafiltration device; the iron phosphate mother liquor treatment module is connected with a liquid inlet of the concentrated water reverse osmosis module through a filtrate pipeline of the second ultrafiltration device; a concentrated water pipeline of the wastewater reverse osmosis module is connected with a liquid inlet of the concentrated water reverse osmosis module; the water producing port is arranged on the wastewater reverse osmosis module; a concentrated water pipeline of the concentrated water reverse osmosis module is connected with a liquid inlet of the evaporative crystallization salt separation system, and a water production pipeline of the concentrated water reverse osmosis module is connected with the wastewater reverse osmosis module; and a cooling water outlet of the evaporation crystallization salt separation system is connected with the concentrated water reverse osmosis module.
7. The iron phosphate wastewater treatment and salt recovery system according to claim 6, wherein the concentrate line of the concentrate reverse osmosis module is further provided with a concentrate line for returning to the first ultrafiltration device.
8. The iron phosphate wastewater treatment and salt recovery system of claim 6, wherein the wastewater reverse osmosis module comprises a primary reverse osmosis device, a secondary reverse osmosis device and a terminal reverse osmosis device which are connected in sequence through a water production pipeline; the iron phosphate rinsing water treatment module is connected with a liquid inlet of the primary reverse osmosis device through a filtrate pipeline of the first ultrafiltration device; the water producing port is arranged on the terminal reverse osmosis device; the concentrated water reverse osmosis module comprises a concentrated water first-stage reverse osmosis device, a concentrated water second-stage reverse osmosis device and a concentration reverse osmosis device; a concentrated water pipeline of the first-stage reverse osmosis device is connected with the concentrated water first-stage reverse osmosis device, and the concentrated water first-stage reverse osmosis device is sequentially connected with the concentrated water second-stage reverse osmosis device and the terminal reverse osmosis device through a water production pipeline; a concentrated water pipeline of the secondary reverse osmosis device is connected with the concentrated water secondary reverse osmosis device; a concentrated water pipeline of the concentrated water primary reverse osmosis device is connected with the concentration reverse osmosis device, and the concentrated water pipeline of the concentration reverse osmosis device is connected with a liquid inlet of the evaporation crystallization salt separation system;
preferably, a concentrate pipeline of the terminal reverse osmosis device is connected with the concentrate secondary reverse osmosis device.
9. The iron phosphate wastewater treatment and salt recovery system according to claim 8, wherein the concentrate line of the concentrate secondary reverse osmosis device is further provided with a concentrate line for returning to the first ultrafiltration device.
10. A method for treating iron phosphate wastewater and recovering salt by using the iron phosphate wastewater treatment and salt recovery system according to any one of claims 1 to 9, comprising: inputting rinsing water in the iron phosphate wastewater to be treated from a rinsing water inlet on the rinsing water regulating device, and inputting mother liquor in the iron phosphate wastewater to be treated from a mother liquor inlet on the mother liquor regulating device; adjusting the pH value in the first mixing and precipitating device to 8-9.5, and adjusting the pH value in the reaction device to 5-6.5; the water producing port of the reverse osmosis module is used for extracting reuse water, and the salt outlet of the evaporative crystallization salt separation system is used for outputting salt;
preferably, when the iron phosphate wastewater treatment and salt recovery system comprises a second mixing and precipitating device, the pH value in the second mixing and precipitating device needs to be adjusted to 8-9.5.
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| CN114835325A (en) * | 2022-05-06 | 2022-08-02 | 四川绿沃创新环保工程有限公司 | Iron phosphate mother liquor and rinsing water recycling treatment process thereof |
| CN115124178A (en) * | 2022-07-21 | 2022-09-30 | 江苏卓博环保科技有限公司 | Recycling treatment device and method for wastewater generated in iron phosphate production by ammonia process |
| CN115448272A (en) * | 2022-09-26 | 2022-12-09 | 深圳永清水务有限责任公司北京分公司 | Recycling treatment process of aged mother liquor in iron phosphate production process |
| CN115521015A (en) * | 2022-10-31 | 2022-12-27 | 南京中电环保集团有限公司 | System and method for treating lithium iron phosphate battery mother liquor wastewater |
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| CN115124178A (en) * | 2022-07-21 | 2022-09-30 | 江苏卓博环保科技有限公司 | Recycling treatment device and method for wastewater generated in iron phosphate production by ammonia process |
| CN115124178B (en) * | 2022-07-21 | 2024-06-11 | 江苏卓博环保科技有限公司 | Recycling treatment device and method for wastewater from ammonia ferric phosphate production |
| CN115448272A (en) * | 2022-09-26 | 2022-12-09 | 深圳永清水务有限责任公司北京分公司 | Recycling treatment process of aged mother liquor in iron phosphate production process |
| CN115448272B (en) * | 2022-09-26 | 2024-02-02 | 深圳永清水务有限责任公司 | Recycling treatment process of aging mother liquor in iron phosphate production process |
| CN115521015A (en) * | 2022-10-31 | 2022-12-27 | 南京中电环保集团有限公司 | System and method for treating lithium iron phosphate battery mother liquor wastewater |
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