CN115991560A - Treatment method for recycling iron phosphate production wastewater - Google Patents
Treatment method for recycling iron phosphate production wastewater Download PDFInfo
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- CN115991560A CN115991560A CN202310282999.2A CN202310282999A CN115991560A CN 115991560 A CN115991560 A CN 115991560A CN 202310282999 A CN202310282999 A CN 202310282999A CN 115991560 A CN115991560 A CN 115991560A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 239000002351 wastewater Substances 0.000 title claims abstract description 44
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 229910000398 iron phosphate Inorganic materials 0.000 title claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 221
- 239000012528 membrane Substances 0.000 claims abstract description 99
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 62
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 50
- 238000011084 recovery Methods 0.000 claims abstract description 46
- 239000012452 mother liquor Substances 0.000 claims abstract description 26
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 17
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 15
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 15
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 11
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 11
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 94
- 239000008213 purified water Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000010802 sludge Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000008237 rinsing water Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 14
- 230000008025 crystallization Effects 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- OYCMCIMILVVEHY-UHFFFAOYSA-N [Mg].[Mn].[Fe] Chemical compound [Mg].[Mn].[Fe] OYCMCIMILVVEHY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for recycling ferric phosphate production wastewater, which comprises the following steps: s1: respectively and sequentially filtering and ultrafiltering the rinse water and the mother liquor to respectively obtain water produced by ultrafiltration of the rinse water and water produced by ultrafiltration of the mother liquor; s2: carrying out primary membrane concentration on the ultrafiltration produced water of washing water to obtain a first concentrated solution and first produced water; concentrating the first concentrated solution by a second-stage membrane to obtain a second concentrated solution and second produced water; mixing the second concentrated solution with mother liquor ultrafiltration produced water, and then carrying out three-stage membrane concentration to obtain a third concentrated solution and third produced water; s3: performing multistage reverse osmosis treatment on the first produced water, the second produced water and the third produced water to obtain reuse water; s4: performing directional special membrane treatment on the third concentrated solution to obtain a first recovered concentrated solution, and performing evaporative crystallization to obtain magnesium sulfate and manganese sulfate; s5: the first recovery produced water obtained in the step S4 is subjected to precipitation treatment to obtain recovery ferric salt; s6: and (5) evaporating and crystallizing the supernatant obtained in the step (S5) to obtain ammonium sulfate and ammonium dihydrogen phosphate.
Description
Technical Field
The invention belongs to the technical field of iron phosphate production wastewater treatment, and particularly relates to a method for recycling iron phosphate production wastewater.
Background
The ferric phosphate is an ideal precursor material of the anode materials of automobile power batteries, power grid energy storage batteries and electric tool batteries, and is an important raw material for the production of new energy batteries. In the production process of ferric phosphate, mother liquor and rinsing water are generated, wherein the mother liquor is acidic inorganic wastewater with high concentration of ammonia nitrogen, sulfate radical and phosphate radical, and the rinsing water contains a small amount of ammonia nitrogen, sulfate radical and phosphate radical. At present, for the waste water in the iron phosphate production, firstly, pretreatment is carried out, a pipe chute sedimentation tank is used for removing metal ions such as calcium, magnesium, manganese and iron in the waste water by adjusting the pH value, then membrane concentration is adopted to obtain concentrated solution, finally, evaporation crystallization is carried out, and ammonium sulfate and ammonium dihydrogen phosphate are obtained by salt separation. During pretreatment, calcium, magnesium, manganese and iron cannot be recovered respectively, and the obtained mixed salt is difficult to recycle and separate. The whole process has larger energy consumption, and the quality of the product water produced by the membrane system is different. During evaporative crystallization, the components in the inlet water are complex, the evaporative crystallizer has a large risk of fouling, and the quality of the byproducts is not high.
Disclosure of Invention
Aiming at the problems, the invention provides a method for recycling ferric phosphate production wastewater, which comprises the following steps:
s1: pretreatment: sequentially filtering and ultrafiltering rinsing water to obtain ultrafiltration water of washing water; sequentially filtering and ultrafiltering the mother liquor to obtain mother liquor ultrafiltration produced water;
s2: membrane concentration: carrying out primary membrane concentration on the ultrafiltration produced water of washing water to obtain a first concentrated solution and first produced water;
concentrating the first concentrated solution by a second-stage membrane to obtain a second concentrated solution and second produced water;
mixing the second concentrated solution with mother liquor ultrafiltration produced water, and then carrying out three-stage membrane concentration to obtain a third concentrated solution and third produced water;
s3: purifying: performing first-stage reverse osmosis on the first produced water to obtain first reverse osmosis concentrated solution and first purified produced water;
mixing the second produced water, the third produced water and the first reverse osmosis concentrated solution, and performing secondary reverse osmosis to obtain a second reverse osmosis concentrated solution and a second purified produced water;
performing three-stage reverse osmosis on the second purified produced water to obtain third reverse osmosis concentrated solution and third purified produced water, wherein the third purified produced water is reused as pure water for production;
s4: magnesium and manganese recovery: performing directional special membrane treatment on the third concentrated solution to obtain a first recovered concentrated solution and first recovered produced water; evaporating and crystallizing the first recovered concentrated solution to obtain magnesium sulfate and manganese sulfate;
s5: and (3) iron recovery: adding ammonia water into the first recovered produced water, and inputting the mixture into a sedimentation tank to obtain a first supernatant and sludge;
the sludge passes through a filtering device to obtain a sludge cake and a second supernatant;
s6: and (3) evaporating and crystallizing: and evaporating and crystallizing the first supernatant to obtain ammonium sulfate, monoammonium phosphate, mixed salt and evaporating condensed water.
According to the treatment method, aiming at the characteristic that the wastewater produced by iron phosphate contains high-concentration ammonium sulfate, a small amount of metal ions and phosphoric acid, firstly, the suspended matters in the wastewater are removed by pretreatment, then the ammonium sulfate in the wastewater is concentrated by membrane concentration, and the produced water is reused for production; separating magnesium and manganese ions in the wastewater by using the directional special membrane, thereby recovering manganese sulfate and magnesium sulfate products; adding a proper amount of ammonia water to adjust the pH value to 4.0-5.0, and removing iron ions in the wastewater, wherein the generated iron-containing sludge can be reused as an iron source of ferric phosphate for production; and (3) feeding the first supernatant after removing the impurities into an evaporative crystallization system, and recovering ammonium sulfate and ammonium dihydrogen phosphate. Thereby realizing the comprehensive recycling treatment of the wastewater from the iron phosphate production, having stable production operation, small occupied area, low operation cost and high side value of the recycled product and realizing the recycling of the wastewater from the iron phosphate production.
Optionally, in step S1, the rinse water is the rinse water generated in the production process of the ferric phosphate, and the temperature is 40-45 ℃; the mother liquor is produced in the production process of ferric phosphate, and the temperature is 60-65 ℃;
ammonia nitrogen, phosphate radical, sulfate radical and Fe in mother liquor 3+ 、F - 、Ca 2+ 、Mg 2+ 、Mn 2+ The concentration of the (C) is high as that of the corresponding component in the rinse water.
Further alternatively, step S1 is specifically that rinse water and mother liquor are respectively collected and adjusted, and are respectively filtered, so that two obtained filtrate and filter cakes, wherein the filter cakes are mainly ferric phosphate, and the two filtrate can be reused in a production workshop, and are respectively cooled to 25-35 ℃, and then are respectively subjected to ultrafiltration to obtain the water produced by ultrafiltration of the rinse water and the water produced by ultrafiltration of the mother liquor.
The filtering device in the step S1 is selected from one or a combination of a plurality of integrated water purifiers, precision filters, plate-and-frame filter presses, disc filters and tubular micro-filtration;
the cooling device is selected from one or a combination of a plurality of open cooling towers, closed cooling towers, plate heat exchangers and tubular heat exchangers;
the ultrafiltration device is one selected from immersed ultrafiltration, internal pressure ultrafiltration and external pressure ultrafiltration, and has an operating pressure of 0.2-0.3Mpa, and the water recovery rate is more than or equal to 90%.
Optionally, in step S2, after the washing water ultrafiltration product water and the second reverse osmosis concentrate are mixed, performing primary membrane concentration;
the primary membrane concentration device and the secondary membrane concentration device both adopt 8MPa seawater membrane elements, and the tertiary membrane concentration device adopts 12MPa ultrahigh pressure membrane elements;
the TDS of the first concentrated solution is 45-50g/L, and the recovery rate is 75% -80%; the TDS of the second concentrated solution is 90-100g/L, and the recovery rate is 50% -65%; the TDS of the third concentrated solution is 160-190g/L, and the recovery rate is 40% -50%.
Preferably, an energy recovery device is arranged in the secondary membrane concentration device and the tertiary membrane concentration device, and the energy of the high-pressure concentrated water side of the membrane component is recovered, so that the flow rate of the high-pressure pump is reduced.
Preferably, the first concentrated solution is firstly input into a cartridge filter, 40-50% of liquid in the cartridge filter flows out to be used as filtrate, and the filtrate is pumped into a secondary membrane concentration device through a high-pressure plunger pump or a multistage centrifugal pump;
and after the energy exchange between the first concentrated solution and the second concentrated solution which are remained in the cartridge filter is carried out through the energy recovery device, the first concentrated solution is input into the secondary membrane concentration device. The energy recovery device is a PX product purchased from an energy recovery company in the United states, and has a pressure resistance of 8Mpa.
Preferably, in the three-stage membrane concentration device, the mixed solution of the second concentrated solution and the mother solution ultrafiltration water is firstly filtered by a cartridge filter, 40-50% of the liquid in the cartridge filter flows out to be used as filtrate, and the filtrate is pumped into the three-stage membrane concentration device through a high-pressure plunger pump or a multistage centrifugal pump;
and after the residual mixed solution in the cartridge filter and the third concentrated solution are subjected to energy exchange through an energy recovery device, the mixed solution is input into a three-stage membrane concentration device, and the pressure of the energy recovery device is 12Mpa.
Optionally, in step S3, after the first produced water and the third reverse osmosis concentrate are mixed, performing first-stage reverse osmosis; mixing the second produced water, the third produced water, the first reverse osmosis concentrated solution and the evaporation condensate water in the step S6, and performing secondary reverse osmosis; and mixing the second purified water and the first purified water, and performing three-stage reverse osmosis.
Before reverse osmosis at each level, raw water passes through a cartridge filter, the pH value of the raw water is adjusted to 6-7 by using ammonia water, and then the raw water is input into reverse osmosis membrane modules at each level.
Optionally, the first-stage reverse osmosis and the second-stage reverse osmosis are both implemented by adopting a brackish water membrane element, the TDS of the first purified water is 200-220mg/L, the TDS of the second purified water is 80-100mg/L, the TDS of the third purified water is not more than 5mg/L, and the third purified water is reused as reuse water for production;
the recovery rate of the first-stage reverse osmosis is not less than 90%, the recovery rate of the second-stage reverse osmosis is not less than 85%, and the recovery rate of the third-stage reverse osmosis is not less than 95%.
Optionally, in step S4, a two-stage directional special membrane is adopted, the removal rate of the membrane system on magnesium and manganese ions reaches 85%, the content of magnesium and manganese ions in the first recovered produced water is not more than 5mg/L, and the concentration of magnesium and manganese ions in the first recovered concentrated solution is 100-120g/L. The evaporated condensate water produced in this step is returned to step S3 and mixed with the first reverse osmosis concentrate.
Optionally, in step S5, ammonia water is added into the first recovered water, the pH value is adjusted to 4-5, the iron ions in the first recovered water form sludge precipitate, the sludge precipitate is filtered for the second time to obtain a mud cake, and the mud cake is mainly ferric hydroxide and/or ferric hydroxy phosphate and can be reused in the front end production line of ferric phosphate;
and (4) returning the second supernatant to the step (S4), mixing with the third concentrated solution, and performing directional special film treatment.
Optionally, the sedimentation Chi Xuanzi inclined tube sedimentation tank and the high-efficiency sedimentation tank are arranged, and the filtering device is selected from a plate-and-frame filter press, a centrifuge and a belt dryer.
Optionally, the evaporation crystallization device in the steps S6 and S5 is an MVR system and/or a multi-effect evaporator, and the TDS of the evaporated condensate water is not more than 350mg/L.
The treatment method comprises the steps of firstly removing suspended matters or fine colloid particles by using a pretreatment system, controlling the pollution indexes of water produced by ultrafiltration of washing water and water produced by ultrafiltration of mother liquor to be less than or equal to 3, then concentrating ammonium sulfate in pretreatment liquid by using a membrane concentration system, purifying the concentrated water to obtain concentrated liquid and pure water with the conductivity less than or equal to 10 mu s/cm, recycling the pure water for production, adding a proper amount of medicament into the concentrated liquid to remove metal impurity ions in the wastewater, finally evaporating and crystallizing the concentrated liquid by using an MVR system to obtain ammonium sulfate and ammonium dihydrogen phosphate products, and refluxing evaporated condensed water to a membrane purification step to prepare the pure water. The method solves the problem of iron phosphate production wastewater pollution, greatly reduces the medicament cost and saves the land area.
According to the characteristic that the concentration of pollutants in the rinsing water is different from that of the mother liquor, the rinsing water and the mother liquor are respectively pretreated, the pretreated rinsing water ultrafiltration produced water is concentrated by a two-stage membrane, the concentration of the pollutants is improved, the second concentrated solution is mixed with the mother liquor ultrafiltration produced water, and then the third-stage membrane concentration is carried out, so that the concentration of the pollutants in the obtained third concentrated solution is higher, and the resource recovery can be carried out. And the third concentrated solution is treated by a directional special film, magnesium ions and manganese ions are concentrated in a directional way, and then the magnesium sulfate and the manganese sulfate are obtained through evaporation and crystallization. The water produced by the directional film is precipitated to obtain ferric salt precipitate (recoverable) and a first supernatant, and the first supernatant is evaporated and crystallized to obtain ammonium sulfate and ammonium dihydrogen sulfate. Thus, the invention respectively recovers magnesium sulfate, manganese sulfate, ferric salt, ammonium sulfate and ammonium dihydrogen sulfate.
The invention uses membrane treatment at a plurality of places, and how to use the produced water of the membrane treatment is also the technical key point in the field. In the invention, the water produced by ultrafiltration of washing water and the water produced by ultrafiltration of mother liquor are respectively utilized as raw materials for membrane treatment in the step 2; the first produced water is used as a raw material for purification in the step S3 to prepare reuse water. Then, the invention rationally utilizes the membrane produced water of each part according to the characteristics of membrane concentration and reverse osmosis produced water of each stage. Specifically, the salt concentration of the second produced water and the third produced water is larger than that of the first produced water, the second produced water and the third produced water are mixed with the first reverse osmosis concentrated solution, and the evaporation condensed water obtained in the step S6 is regulated, and then the second reverse osmosis is carried out; the salt concentration of the second reverse osmosis concentrated solution is mixed with water produced by ultrafiltration of washing water, and the mixture is subjected to primary membrane concentration; the salt concentration of the second purified water and the salt concentration of the first purified water are different, but are lower, the second purified water and the first purified water are mixed and then subjected to three-stage reverse osmosis, and the obtained third purified water can be used as reuse water, for example, the third purified water is mixed with the first purified water, the salt concentration is regulated, and then the first-stage reverse osmosis is performed.
Because the invention relates to multi-channel membrane treatment, the transportation and mixing of various produced water and concentrated solutions are correspondingly carried out, especially, the concentration of salt in some concentrated solutions is larger, the invention is not friendly to pipelines for transporting the concentrated solutions at normal temperature, the crystallization condition is serious when the pipelines run, the pollution and blockage risk is high, and the production and maintenance are stopped frequently. The invention provides a small portable dredger, which is used for processing crystals in a pipeline in real time and prolonging the production period.
Optionally, a dredger is arranged in the water production and concentrated solution pipeline after each level of membrane treatment, the dredger comprises a traction rope and a rotating body, the rotating body comprises a central plate and a plurality of spiral blades at two sides of the central plate, the central plate is perpendicular to the water flow direction in the pipeline, a through hole is arranged in the center, the traction rope penetrates through the through hole, and the rotating body is connected to the traction rope in a sliding manner;
the spiral blades on any side of the central plate are uniformly arranged in sequence along the circumferential direction of the central plate in an inclined manner; the side of the helical blade, which is close to the pipe wall, is the outer side, the outer side is provided with an arc, and the distance between the widest part of the outer side of the helical blade and the inner wall of the pipeline is smaller, so that when the helical blade rotates, solid crystals deposited on the inner wall are scraped.
Further alternatively, one side of the central plate faces the upstream direction of the pipeline, and the other side faces the downstream direction of the pipeline, and the spiral blades are uniformly distributed on two sides of the central plate respectively;
each spiral vane has an arc shape and protrudes toward the adjacent spiral vane.
Further optionally, the hauling rope comprises fixing parts at two ends and a straight part in the middle, and the hauling rope is a thin steel wire or rope; the fixing part is arranged at two pipe orifices of the pipeline and comprises two thin steel wires or ropes which are respectively fixed at the pipe orifices of the pipeline, so that the end part of the straight part is positioned at the circle center of the pipeline, namely the fixing frame penetrates through the circle center of the pipeline along the radial direction of the pipe orifices;
the straight portion is located at the center of the pipe and is parallel to the pipe.
Further optionally, the traction rope is composed of two thin steel wires or two ropes, and the two thin steel wires or the two ropes in the fixing part are separated and respectively fixed at the pipe orifice of the pipeline; the straight portions are twisted with each other in the form of two strands of thin wire or ropes, which shaping helps to promote rotation of the center plate as it moves along the straight portions.
When the water flow in the pipeline is vertical or inclined upwards, the rotating body can ascend under the action of the water flow, when the water flow force is smaller than the gravity of the rotating body, the rotating body naturally falls down, and the pipe wall can be cleaned in the ascending and descending processes without power equipment. If the rotating body needs to be controlled to move back and forth in the pipeline in real time, a power device can be arranged on the downstream side of the rotating body, the power device can move back and forth along the straight part and push the rotating body to move at the same time, the rotating body moves along the water flow direction under the action of water flow and pushes the power device to move together, and when the rotating body needs to move reversely, the power device pushes the rotating body to move reversely.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling wastewater from iron phosphate production in example 1;
fig. 2 is a schematic structural view of the dredge device of example 6.
In the drawings, 1-hauling ropes, 2-rotating bodies, 3-center plates, 4-spiral blades and 5-pipelines.
Detailed Description
The raw material wastewater used in the following examples and comparative examples is iron phosphate production wastewater of an enterprise, the iron phosphate production of the enterprise adopts an ammonia process, hydrogen peroxide is added into ferrous sulfate to oxidize ferrous iron into ferric iron, the pH value of the reaction is controlled by adding ammonia water, iron phosphate is synthesized, and the aging is carried out by phosphoric acid. Two types of wastewater are generated in the production process of ferric phosphate, namely mother liquor and rinse water, and the water quality and the water quantity are shown in the following table:
TABLE 1 Components of wastewater from iron phosphate production
| Index (I) | Mother liquor | Rinse water | Unit (B) |
| Water volume | 2000 | 3500 | m 3 Day/day |
| Ammonia nitrogen content | 13000 | 1200 | mg/L |
| Phosphate radical | 8000 | 1500 | mg/L |
| Sulfate radical | 60000 | 6000 | mg/L |
| Fe 3+ | 50 | 5 | mg/L |
| F - | 50 | 20 | mg/L |
| Ca 2+ | 40 | 5 | mg/L |
| Mg 2+ | 800 | 100 | mg/L |
| Mn 2+ | 200 | 30 | mg/L |
| Temperature (temperature) | 60 | 45 | ℃ |
Example 1
The invention provides a method for recycling ferric phosphate production wastewater, which is shown in figure 1 and comprises the following steps:
s1: pretreatment: respectively collecting and adjusting the rinse water and the mother liquor, and respectively lifting to a plate-and-frame filter press by a pump to perform preliminary filtration to obtain two kinds of filtrate and a filter cake;
the two filtrates are respectively subjected to cooling treatment by a secondary plate heat exchanger, and the temperature after cooling is 25-30 ℃; then, respectively feeding the two filtrates into an ultrafiltration device, ultrafiltering with a hollow fiber ultrafiltration membrane under the operation pressure of 0.3Mpa, and automatically performing gas-water combined backwashing every 40min by the ultrafiltration device, and performing manual chemical cleaning after the ultrafiltration device is operated for 6 months so as to maintain the long-term stable operation of the ultrafiltration membrane; returning ultrafiltration backwash water to the regulating tank for reprocessing;
s2: membrane concentration: after the washing water ultrafiltration produced water and the second reverse osmosis concentrated solution are mixed, pumping the mixture into a security filter through a booster pump, adding a reducing agent (sodium bisulphite), controlling the oxidation-reduction potential (ORP) of the inlet water entering a primary membrane concentration device to be less than or equal to 350mv, and enabling the outlet water of the security filter to enter the primary membrane concentration device for primary membrane concentration;
the primary membrane concentration device is an 8MPa seawater membrane element, adopts multi-section connection, is provided with a pressure-resistant 4MPa interstage booster pump in the middle, and obtains a first concentrated solution and first produced water through the primary membrane concentration device, wherein the recovery rate of primary membrane concentration is 80 percent, and the concentration of concentrated solution is 4.5 percent;
pumping the first concentrated solution into a cartridge filter through a booster pump, enabling 50% of liquid in the cartridge filter to flow out as filtrate, and pumping the filtrate into a secondary membrane concentration device through a high-pressure plunger pump; exchanging energy with the second concentrated solution through an energy recovery device by using the first concentrated solution of which the residual content is 50 percent of the cartridge filter, and pumping the first concentrated solution of which the residual content is 50 percent of the cartridge filter into a secondary membrane concentration device after recovering the energy by using the high-pressure energy of the second concentrated solution; the energy recovery device saves more than 50% of electric energy; the energy recovery device is a PX product purchased from an energy recovery company in the United states, and has a pressure resistance of 8Mpa;
the second-stage membrane concentration device is an 8MPa seawater membrane element, is connected in a multi-stage mode, an interstage booster pump with the pressure of 8MPa is arranged in the middle of the second-stage membrane concentration device, second concentrated solution and second produced water are obtained through the second-stage membrane concentration device, the recovery rate of the second-stage membrane concentration is 50%, and the ammonium sulfate concentration of the first concentrated solution is concentrated to 9% by the second-stage membrane concentration device; the second concentrated solution enters a mother solution ultrafiltration water producing tank after passing through an energy recovery device;
after the second concentrated solution is mixed with the mother solution ultrafiltration produced water, pumping the mixture into a cartridge filter through a booster pump, enabling 50% of liquid in the cartridge filter to flow out to serve as filtrate, and pumping the filtrate into a three-stage membrane concentration device through a high-pressure plunger pump; the remaining 50% of the second concentrated solution and mother solution ultrafiltration water-producing mixed solution of the cartridge filter exchanges energy with the third concentrated solution through an energy recovery device, the high-pressure energy of the third concentrated solution is utilized to recover the energy, and after the energy is recovered, the remaining 50% of the second concentrated solution and mother solution ultrafiltration water-producing mixed solution of the cartridge filter is also pumped into a three-stage membrane concentration device, and the energy can be saved by more than 50% through the energy recovery device;
the three-stage membrane concentration device (12 MPa ultrahigh pressure membrane element) adopts multi-stage connection, an interstage booster pump with the pressure resistance of 12MPa is arranged in the middle, three-stage membrane concentration is carried out to obtain a third concentrated solution and third produced water, the recovery rate of the three-stage membrane concentration is 50%, and the ammonium sulfate concentration of the second concentrated solution and the mother solution ultrafiltration produced water is concentrated to 16% by utilizing the three-stage membrane concentration;
s3: and (3) membrane purification: after the first produced water and the third reverse osmosis concentrated solution are mixed, pumping the mixture into a cartridge filter through a booster pump, adding ammonia water, controlling the pH value to be 6-7, enabling the liquid discharged from the cartridge filter to enter a first-stage reverse osmosis device, and obtaining the first reverse osmosis concentrated solution and the first purified produced water through first-stage reverse osmosis, wherein the recovery rate is 90%, and the TDS of the first purified produced water is 200mg/L;
mixing the second produced water, the third produced water, the first reverse osmosis concentrated solution and the evaporated condensate water in the step S6, pumping the mixture into a security filter through a booster pump, adding ammonia water, controlling the pH value to be 6-7, enabling the liquid out of the security filter to enter a secondary reverse osmosis device, and obtaining the second reverse osmosis concentrated solution and the second purified produced water through secondary reverse osmosis, wherein the recovery rate is 85%, and the TDS of the second purified produced water is 100mg/L;
after the second purified water and the first purified water are mixed, pumping the mixed water into a security filter through a booster pump, adding a bactericide, enabling the liquid discharged from the security filter to enter a three-stage reverse osmosis device, obtaining third reverse osmosis concentrated liquid and third purified water through three-stage reverse osmosis, wherein the recovery rate is 95%, and the TDS of the third purified water is 5mg/L;
primary reverse osmosis, secondary reverse osmosis and tertiary reverse osmosis are all implemented by brackish water membrane elements;
s4: magnesium and manganese recovery: pumping the third concentrated solution into a cartridge filter through a booster pump, and allowing the liquid discharged from the cartridge filter to enter a primary directional special membrane group for treatment (YX-CuT 100-40 membrane of Indonesia environmental technology Co., in Guangdong), wherein the recovery rate is 90% and the concentration of the concentrated solution is 8%; pumping the produced water of the primary directional special membrane group into a security filter through a booster pump, and treating the effluent of the security filter into a secondary directional special membrane group to obtain a first recovered concentrated solution and first recovered produced water, wherein the content of magnesium and manganese ions in the first recovered produced water is not more than 5mg/L;
the first recovery concentrated solution enters an evaporation crystallization device, and magnesium sulfate and manganese sulfate products are obtained through evaporation crystallization;
s5: and (3) iron recovery: adding ammonia water into the first recovered produced water to adjust the pH value to 4.0-5.0, and inputting the solution into a sedimentation tank to obtain a first supernatant and sludge;
the sludge passes through a plate-frame filter pressing device to obtain a sludge cake and a second supernatant, the second supernatant flows back to the step S4, is mixed with a third concentrated solution, and is subjected to directional special membrane treatment;
s6: and (3) evaporating and crystallizing: and (3) enabling the first supernatant to enter an evaporative crystallization system after passing through a precise filter, and performing evaporative crystallization to obtain ammonium sulfate, monoammonium phosphate, mixed salt and evaporative condensate water.
The cartridge filter cartridges of the cartridge filter adopt 5 mu m large flux folding cartridges. The evaporation crystallization device adopts secondary falling film evaporation and is matched with primary forced circulation; the material density of the two-effect falling film separator is controlled to be less than or equal to 1.2kg/L, and the material density of the forced circulation separator is controlled to be less than or equal to 1.45kg/L.
Comparative example 1
The treatment method for recycling the iron phosphate production wastewater of the comparative example comprises the steps of respectively treating rinsing water and mother liquor by using the method provided by patent CN201510024842.5, namely, regulating the pH value by adding ammonia water, performing impurity removal pretreatment, performing multistage membrane concentration, performing multistage membrane purification, and finally performing evaporation and crystallization treatment to obtain ammonium salt and mixed salt.
Comparative example 2
The treatment method for recycling the iron phosphate production wastewater of the comparative example is the same as that of comparative example 1, except that the comparative example does not include the pretreatment step of adjusting the pH value with ammonia water and removing impurities.
The product of ammonium sulfate, monoammonium phosphate, magnesium sulfate and manganese sulfate is identified, wherein the ammonium sulfate product meets the requirement of the standard of industrial grade ammonium sulfate (HG/T5744-2020), and nitrogen (N)) Content (on a dry basis) ω/% was 20.6%; the monoammonium phosphate meets the requirements of GB10205-2009 monoammonium phosphate and diammonium phosphate, and the traditional method is the first grade: total nutrient (N+P) 2 O 5 ) The mass fraction of (2) is more than or equal to 55%, and the water content is less than or equal to 4%; magnesium sulfate meets the requirements of magnesium sulfate standard (HG/T2680-2017), class I first class product, magnesium sulfate (MgSO) 4 ·7H 2 O) content is more than or equal to 99%; manganese sulfate meets the requirements of the standard of manganese sulfate (HG/T2962-2010), and manganese sulfate (MnSO 4 ·H 2 The content of O) is more than or equal to 98 percent.
Table 2 comparison of the process flows and operating costs for example 1 and comparative examples 1, 2
| Project | Example 1 | Comparative example 1 | Comparative example 2 |
| Total treated water quantity (m) 3 Day/sky | 5500 | 5500 | 5500 |
| Floor area (m) 2 ） | 5000 | 8000 | 5000 |
| Evaporated water amount (m) 3 Day/sky | 60 | 75 | 60 |
| Investment cost (Wanyuan) | 8500 | 9000 | 7500 |
| Running cost (Yuan/m) 3 ） | 40.52 | 53.87 | 36.65 |
| Byproduct profits (yuan/m) 3 ） | 39.10 | 29.18 | 17.34 |
| Total running cost (yuan/m) 3 ） | 1.42 | 24.69 | 19.31 |
As can be seen from the above table, the treatment method provided by the invention has better economic benefits, and is characterized by small occupied area, small evaporation water quantity, high byproduct benefits and low total operation cost. In the embodiment 1, after the wastewater is concentrated, magnesium-manganese-iron recovery is carried out, the water quantity entering the metal recovery process is only 1/5-1/4 of the water quantity when the front end is recovered, so that the occupied area of the metal recovery process is reduced, the dosage of the medicament is reduced, the equipment model specification and the corresponding civil engineering structure specification are reduced, and the dosage of the medicament is greatly reduced because the pH value of the magnesium-manganese in the recovered wastewater is not required to be regulated by adding the medicament, thereby greatly reducing the related investment and operation cost, and simultaneously respectively recovering and utilizing the magnesium-manganese and iron metals in the wastewater, and increasing the byproduct value. In comparative example 2, the impurity content of the by-product of the evaporative crystallization is high, the purity is low, and the value of the by-product is low because the impurity removal is not performed.
Example 2
The treatment method for recycling the wastewater from iron phosphate production in the embodiment is the same as that in embodiment 1, except that in step S2, all the first concentrated solution is filtered by a cartridge filter, and all the filtrate obtained after filtration is input into a secondary membrane concentration device, so that energy recovery is not performed;
the second concentrated solution and the mother solution ultrafiltration water-producing mixed solution are all filtered by a cartridge filter, and all filtrate obtained after filtration is input into a three-stage membrane concentration device without energy recovery.
In the embodiment 1, the step S2 saves more than 50% of the electric energy by using the energy recovery device, but the embodiment does not save the electric energy.
Example 3
The treatment method for recycling the wastewater from iron phosphate production in this embodiment is the same as that in embodiment 2, except that in step S2, the first concentrated solution is directly input into the secondary membrane concentration device without passing through a cartridge filter; the second concentrated solution and the mother solution ultrafiltration water-producing mixed solution are directly input into the three-stage membrane concentration device without passing through a cartridge filter.
In the embodiment, no cartridge filter is arranged, so that the impurities of the first concentrated solution, the second concentrated solution and the mother solution ultrafiltration water-producing mixed solution are more, the second-stage membrane concentration device and the third-stage membrane concentration device are easy to be blocked, and the actual operation period is shortened by 20% compared with that of the embodiment 2.
Example 4
The treatment method for recycling the wastewater from iron phosphate production in this embodiment is the same as that in embodiment 1, except that in step S2, only the ultrafiltration water produced from the washing water is subjected to the primary membrane concentration, and the ultrafiltration water produced from the washing water is not mixed with the second reverse osmosis concentrate. Because the salt concentration of the second reverse osmosis concentrated solution is not high, the step S4 is not needed to dilute the third concentrated solution; the first water production in the step S3 is not needed to be carried out, otherwise, the load of the first-stage reverse osmosis is increased; the second reverse osmosis concentrated solution can only be treated separately, so that redundant wastewater is discharged.
Example 5
The treatment method for recycling the wastewater from iron phosphate production in this embodiment is the same as that in embodiment 1, except that in step S3, only the second purified water is subjected to three-stage reverse osmosis, and the second purified water is not mixed with the first purified water. The salt concentration of the first purified produced water does not reach the reuse water standard, and the first produced water cannot be returned; however, the salinity of the first purified water is not high, the third concentrated solution cannot be diluted in the step S4, and the diluted washing water ultrafiltration water cannot be diluted in the step S2; the first purified produced water can only be treated separately, so that redundant waste water is discharged.
Example 6
The treatment method for recycling the waste water of the iron phosphate production is the same as that of the embodiment 1, and is characterized in that a dredge is arranged in a water production and concentrated solution pipeline 5 after concentration of each level of membranes, reverse osmosis and special directional membranes, and as shown in fig. 2, the dredge comprises a traction rope 1 and a rotating body 2, the rotating body 2 comprises a central plate 3 and a plurality of helical blades 4 at two sides of the central plate, the central plate 3 is perpendicular to the water flow direction in the pipeline 5, a through hole is arranged in the center, the traction rope 1 penetrates through the through hole, and the rotating body 2 is connected on the traction rope 1 in a sliding manner;
the helical blades 4 on any side of the central plate 3 are uniformly arranged in sequence along the circumferential direction of the central plate 3 in an inclined manner; the side of the helical blade 4 close to the pipe wall is the outside, and the outside has the radian, and the distance between the widest department of helical blade 4 outside and the inner wall of pipeline 5 is 5mm for when helical blade 4 rotates, strike off the solid crystal of deposit on the inner wall.
One side of the central plate 3 faces the upstream direction of the pipeline 5, the other side faces the downstream direction of the pipeline 5, and the spiral blades 4 are uniformly distributed on two sides of the central plate 3 respectively;
each helical blade 4 itself has a curvature and projects in the direction of the adjacent helical blade 4.
Under the action of water flow in the pipeline 5, the dredger moves along the traction rope 1 along the water flow direction at the same time, the shape of the spiral blades 4 enables all the spiral blades 4 to drive the central plate 3 to rotate in the vertical direction under the action of water flow, the rotation of the spiral blades 4 also promotes water flow disturbance, and conversely, the dredger is promoted to rotate in the vertical direction, so that too thick crystals deposited on the inner wall of the pipeline 5 are scraped off and flushed away along with the water flow. The surface of the helical blade 4 is smooth, and crystals are not easy to adhere during the rapid rotation, and even if a very small amount of crystals adhere, the crystals can be thrown off along with the rotation.
The traction rope 1 comprises fixing parts at two ends and a straight part in the middle, and the traction rope 1 is a thin steel wire; the fixing part is arranged at the pipe orifices at the two ends of the pipeline 5 and comprises two thin steel wires which are respectively fixed at the pipe orifices of the pipeline 5, so that the end part of the straight part is positioned at the center of the pipeline 5, namely the fixing frame penetrates through the center of the pipeline 5 along the radial direction of the pipe orifices;
the straight portion is in the center of the pipe 5 and is parallel to the pipe 5.
Example 7
The treatment method for recycling the wastewater generated in the iron phosphate production of the embodiment is the same as that of the embodiment 6, and is characterized in that the haulage rope 1 is composed of two thin steel wires, and the two thin steel wires in the fixing part are separated and respectively fixed at the pipe orifice of the pipeline 5; the straight portion is a twisted winding of two strands of thin wire with each other, and this shaping helps to promote rotation of the centre plate 3 as the centre plate 3 moves along the straight portion.
The dredge device is used in the embodiments 6 and 7, the condition of pipeline structure or dirt blockage is greatly relieved, the average cleaning maintenance period of the pipeline in the embodiment 1 is 3 months, the average cleaning maintenance period of the pipeline in the embodiment 6 is 6 months, and the average cleaning maintenance period of the pipeline in the embodiment 7 is 7 months after long-time operation experiment.
Claims (8)
1. The method for recycling the wastewater from the iron phosphate production is characterized by comprising the following steps of:
s1: pretreatment: sequentially filtering and ultrafiltering rinsing water to obtain ultrafiltration water of washing water; sequentially filtering and ultrafiltering the mother liquor to obtain mother liquor ultrafiltration produced water;
s2: membrane concentration: carrying out primary membrane concentration on the ultrafiltration produced water of washing water to obtain a first concentrated solution and first produced water;
concentrating the first concentrated solution by a second-stage membrane to obtain a second concentrated solution and second produced water;
mixing the second concentrated solution with mother liquor ultrafiltration produced water, and then carrying out three-stage membrane concentration to obtain a third concentrated solution and third produced water;
s3: purifying: performing first-stage reverse osmosis on the first produced water to obtain first reverse osmosis concentrated solution and first purified produced water;
mixing the second produced water, the third produced water and the first reverse osmosis concentrated solution, and performing secondary reverse osmosis to obtain a second reverse osmosis concentrated solution and a second purified produced water;
performing three-stage reverse osmosis on the first purified water and the second purified water to obtain third reverse osmosis concentrated solution and third purified water;
s4: magnesium and manganese recovery: performing directional special membrane treatment on the third concentrated solution to obtain a first recovered concentrated solution and first recovered produced water; evaporating and crystallizing the first recovered concentrated solution to obtain magnesium sulfate and manganese sulfate;
s5: and (3) iron recovery: adding ammonia water into the first recovered produced water, and inputting the mixture into a sedimentation tank to obtain a first supernatant and sludge;
the sludge passes through a filtering device to obtain a sludge cake and a second supernatant;
s6: and (3) evaporating and crystallizing: and evaporating and crystallizing the first supernatant to obtain ammonium sulfate, monoammonium phosphate, mixed salt and evaporating condensed water.
2. The method for recycling ferric phosphate production wastewater according to claim 1, wherein step S1 is specifically that rinse water and mother liquor are respectively collected and adjusted, respectively filtered to obtain two filtrates and a filter cake, respectively cooled to 25-35 ℃, and then respectively ultrafiltered to obtain water produced by ultrafiltration of the rinse water and water produced by ultrafiltration of the mother liquor.
3. The method for recycling ferric phosphate production wastewater according to claim 1, wherein in the step S2, the primary membrane concentration is performed after the washing water ultrafiltration produced water and the second reverse osmosis concentrated solution are mixed.
4. The method for recycling the wastewater from iron phosphate production according to claim 3, wherein an energy recovery device is arranged in the secondary membrane concentration device and the tertiary membrane concentration device, the energy of the high-pressure concentrated water side of the membrane assembly is recovered, and the flow rate of the high-pressure pump is reduced.
5. The method for recycling the waste water generated in the iron phosphate production according to claim 4, wherein the first concentrated solution is firstly input into a cartridge filter, 40-50% of the liquid in the cartridge filter flows out as filtrate, and the filtrate is pumped into a secondary membrane concentration device through a high-pressure plunger pump or a multistage centrifugal pump;
and after the energy exchange between the first concentrated solution and the second concentrated solution which are remained in the cartridge filter is carried out through the energy recovery device, the first concentrated solution is input into the secondary membrane concentration device.
6. The method for recycling the waste water generated in the iron phosphate production according to claim 5, wherein the mixed solution of the second concentrated solution and the mother solution ultrafiltration water is firstly filtered by a cartridge filter, 40-50% of the liquid in the cartridge filter flows out as filtrate, and the filtrate is pumped into a three-stage membrane concentration device through a high-pressure plunger pump or a multistage centrifugal pump;
and after the residual mixed liquid in the cartridge filter and the third concentrated liquid are subjected to energy exchange through the energy recovery device, the mixed liquid is input into the three-stage membrane concentration device.
7. The method for recycling ferric phosphate production wastewater according to claim 1, wherein in the step S3, the first produced water and the third reverse osmosis concentrated solution are mixed and then subjected to the first stage reverse osmosis; mixing the second produced water, the third produced water, the first reverse osmosis concentrated solution and the evaporation condensate water in the step S6, and performing secondary reverse osmosis; and mixing the second purified water and the first purified water, and performing three-stage reverse osmosis.
8. The method for recycling the wastewater generated in the iron phosphate production according to claim 1, wherein in the step S5, ammonia water is added into the first recovered water, the pH value is adjusted to be 4-5, iron ions in the first recovered water form sludge precipitate, the sludge precipitate is subjected to secondary filtration to obtain a mud cake, and the mud cake is mainly ferric hydroxide and/or ferric hydroxy phosphate and can be reused in a front-end production line of the ferric phosphate;
and (4) returning the second supernatant to the step (S4), mixing with the third concentrated solution, and performing directional special film treatment.
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