CN115448272B - Recycling treatment process of aging mother liquor in iron phosphate production process - Google Patents
Recycling treatment process of aging mother liquor in iron phosphate production process Download PDFInfo
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- CN115448272B CN115448272B CN202211172930.6A CN202211172930A CN115448272B CN 115448272 B CN115448272 B CN 115448272B CN 202211172930 A CN202211172930 A CN 202211172930A CN 115448272 B CN115448272 B CN 115448272B
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 62
- 230000032683 aging Effects 0.000 title claims abstract description 61
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 229910000398 iron phosphate Inorganic materials 0.000 title claims description 24
- 239000012528 membrane Substances 0.000 claims abstract description 95
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 33
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 33
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 33
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 26
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 26
- 238000001704 evaporation Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 158
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 88
- 239000000706 filtrate Substances 0.000 claims description 50
- 239000012065 filter cake Substances 0.000 claims description 38
- 238000000108 ultra-filtration Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 22
- -1 phosphate radical ion Chemical class 0.000 claims description 19
- 230000001105 regulatory effect Effects 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 238000003825 pressing Methods 0.000 claims description 15
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052567 struvite Inorganic materials 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- 235000014413 iron hydroxide Nutrition 0.000 claims 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000007781 pre-processing Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000010413 mother solution Substances 0.000 abstract 3
- 239000004254 Ammonium phosphate Substances 0.000 abstract 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019289 ammonium phosphates Nutrition 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 7
- 239000002519 antifouling agent Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012958 reprocessing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229940085991 phosphate ion Drugs 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 102220008138 rs12252 Human genes 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a recycling treatment process of aging mother liquor in the production process of ferric phosphate, which comprises the following specific steps: s1, preprocessing; s2, membrane concentration treatment; s3, phosphorus recovery treatment; s4, evaporating and crystallizing. Aiming at an aging mother solution in the production process of ferric phosphate, the method firstly adopts pretreatment to remove metal impurities in the aging mother solution, and then concentrates ammonium phosphate and ammonium sulfate in the liquid to 16-19%; and recycling phosphate radical in the wastewater by utilizing ferric salt, and finally centrifugally separating ammonium sulfate with nitrogen content more than or equal to 20.5% by an evaporation system, and returning the centrifugally separated mother solution to the evaporation crystallization system. Thereby realizing the purpose of optimizing the aging mother liquor resources. The method has the advantages of stable production operation, high recycling degree, less impurity content of the recovered ferric phosphate, uniform formed crystal particles, high product side value and capability of being directly reused in a production workshop for preparing battery grade ferric phosphate, and can form a closed chain with the production workshop to the greatest extent, thereby realizing recycling of the aging mother liquor in the production of ferric phosphate.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a recycling treatment process of aging mother liquor in the production process of ferric phosphate.
Background
Iron phosphate is an ideal precursor material for the positive electrode material of automobile power batteries, power grid energy storage batteries and electric tool batteries.
At present, an ammonia process is mainly adopted for preparing ferric phosphate, ferrous sulfate is firstly utilized to add hydrogen peroxide to oxidize ferrous iron into ferric iron, then ferrous iron is reacted with monoammonium phosphate/diammonium phosphate, the pH value of the reaction is controlled by adding ammonia water, ferric phosphate is synthesized, and then aging is carried out through phosphoric acid. Four types of wastewater are generated in the production process of ferric phosphate, and are respectively oxidation mother liquor, oxidation washing water, aging mother liquor and aging washing water, wherein: the aging mother liquor mainly contains a large amount of phosphoric acid, a small amount of ammonium sulfate and a small amount of metal ions, the oxidation mother liquor mainly contains a large amount of ammonium sulfate, a small amount of heavy metal ions and phosphate ions, and the oxidation washing water and the aging washing water mainly contain a small amount of heavy metal ions, low-concentration phosphate ions and ammonium sulfate.
For the aging mother liquor in the production process of the ferric phosphate, the prior treatment process of zero discharge of wastewater is mainly adopted, namely, pretreatment is firstly adopted to remove impurities, a diagonal tube sedimentation tank is mainly adopted to remove metal ions such as calcium, magnesium, manganese and iron in the wastewater by adjusting pH, then membrane concentration is adopted to obtain concentrated solution, and finally evaporation crystallization and salt separation are carried out to obtain ammonium sulfate and ammonium dihydrogen phosphate. Although the treatment process can solve the pollution problem of the aging mother liquor in the production process of the ferric phosphate, the treatment process also has the following defects: the phosphate radical in the wastewater is utilized to remove other metal ions, so that the side value of the phosphate radical is greatly reduced, the side value of the metal ions is also reduced, the development of the treatment process is limited, and the wastewater treatment cost is increased in a phase-changing manner.
Disclosure of Invention
The invention aims to: aiming at the defects of the process for treating the aging mother liquor in the iron phosphate production process, in order to further recover the phosphorus resources in the aging mother liquor in the iron phosphate production process, the method realizes the maximization of the byproduct value while treating the wastewater, reduces the mother liquor treatment cost and improves the competitiveness of the production process, and the invention discloses a recycling treatment process of the aging mother liquor in the iron phosphate production process.
A recycling treatment process of aging mother liquor in the production process of ferric phosphate,
firstly, preprocessing, removing metal impurities in aging mother liquor, and controlling the SDI (silt density index) value of ultrafiltration produced water obtained by preprocessing within 3;
then concentrating ammonium dihydrogen phosphate and ammonium sulfate in the pretreated liquid by using a membrane to obtain a concentrated solution with the concentration of 16% -19% of ammonium dihydrogen phosphate and ammonium sulfate and pure water with the conductivity less than or equal to 10 mu s/cm, wherein the pure water is reused for production;
then adding hydrogen peroxide and ferrous salt into the concentrated solution to recover phosphorus in the solution;
and finally, evaporating and crystallizing the sulfate by using an MVR system to obtain an ammonium sulfate product.
The pollution factors with economic benefits in the mother liquor wastewater are recycled while the pollution problem of the aging mother liquor in the production of ferric phosphate is solved, so that good social and economic benefits are obtained.
The technical scheme is as follows: a recycling treatment process of aging mother liquor in the production process of ferric phosphate comprises the following specific steps:
s1, pretreatment:
s11, introducing aging mother liquor in the production process of ferric phosphate into a raw water regulating tank;
s12, lifting the aging mother liquor in the step S11 to a high-efficiency sedimentation tank through a pump, adding a proper amount of inorganic alkali into the high-efficiency sedimentation tank while stirring, adjusting the pH value of the aging mother liquor to 8.0-8.5, continuously stirring for at least 30 minutes, and introducing the treated aging mother liquor into a plate-and-frame filter press, and respectively obtaining a primary filter cake and a primary filtrate after filter pressing;
s13, introducing the primary filtrate separated in the step S12 into a first reaction tank, then adding a proper amount of inorganic acid aqueous solution into the first reaction tank, regulating the pH value to 5.0-5.5, and then introducing the primary filtrate into a plate heat exchanger to cool to 25-30 ℃;
s14, introducing the primary filtrate treated in the step S13 into an ultrafiltration system to obtain ultrafiltration produced water;
s2, membrane concentration treatment:
introducing ultrafiltration produced water into a two-stage membrane concentration reverse osmosis system to obtain concentrated solution with the mass concentration of 16% -19% and produced water, preparing pure water by the produced water through a two-stage purification reverse osmosis device again, and recycling the pure water for production, wherein:
the main components of the solute of the concentrated solution are ammonium dihydrogen phosphate and ammonium sulfate;
s3, phosphorus recovery treatment:
s31, introducing the concentrated solution obtained in the step S2 into a second reaction tank, stirring, adding an oxidant and an inorganic ferrous salt aqueous solution into the second reaction tank while adding a proper amount of inorganic alkali, regulating the pH value to 1.2-2.0, continuously stirring for at least 30 minutes, and introducing the treated concentrated solution into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a secondary filter cake and a secondary filtrate;
s32, introducing the secondary filtrate separated in the step S31 into a third reaction tank, adding inorganic alkali into the third reaction tank while stirring, adjusting the pH value of the secondary filtrate to 5.5-6.0, continuously stirring for at least 30 minutes, introducing the treated secondary filtrate into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a tertiary filter cake and a tertiary filtrate;
s4, evaporating and crystallizing:
and (3) introducing the tertiary filtrate obtained in the step (S32) into an MVR evaporation crystallization device, and centrifugally separating to obtain a product with the main component of ammonium sulfate.
Further, the total dissolved solids of the aging mother liquor in the iron phosphate production process in step S11 is 42000-56000 mg/L, and the pH value is 1.2-2.0, wherein:
the concentration of phosphate radical ion is 30000-40000 mg/L;
the concentration of ammonium ions is 4000-6000 mg/L;
the concentration of sulfate ions is 8000-10000 mg/L;
the concentration of iron ions is 50-100 mg/L;
the concentration of magnesium ions is 5-10 mg/L;
the concentration of manganese ions is 5-10 mg/L;
the concentration of calcium ions is 0-1 mg/L.
In step S12, the inorganic base is ammonia water, and the primary filter cake mainly comprises magnesium ammonium phosphate and calcium phosphate. The primary filter cake can be sold as a calcium magnesium phosphate fertilizer product after being dried.
Further, in the step S13, the aqueous solution of inorganic acid is an aqueous solution of sulfuric acid with a mass concentration of 20% -98%.
Further, the ultrafiltration system in the step S14 carries out air-water combined backwashing for 1-2 minutes every 40-50 minutes, and ultrafiltration backwash water returns to the raw water regulating tank for reprocessing; and is also provided with
The ultrafiltration system is chemically cleaned every 3-6 months. To maintain long-term stable operation of ultrafiltration.
Further, the SDI value of the ultrafiltration produced water obtained in the step S14 is less than or equal to 3.
Further, the two-stage membrane concentration reverse osmosis system in step S2 includes a first-stage membrane concentration reverse osmosis system and a second-stage membrane concentration reverse osmosis system which are sequentially connected in series, wherein:
the first stage membrane concentration reverse osmosis system comprises:
a first stage booster pump;
the output end of the first stage booster pump is connected with the input end of the cartridge filter;
the output end of the cartridge filter is connected with the input end of the high-pressure pump;
the output end of the high-pressure pump is connected with the input end of the first-stage reverse osmosis filter;
the output end of the first-stage reverse osmosis filter is connected with the input end of the second-stage first-stage reverse osmosis filter through a pipeline, and an intersegmental booster pump is arranged on the pipeline;
the output end of the two sections of the first-stage reverse osmosis filters and the output end of the security filter are respectively connected with the input end of the energy exchange device, and the output end of the energy exchange device is connected with the input end of the first section of the first-stage reverse osmosis filter;
the second-stage membrane concentration reverse osmosis system comprises:
a second stage booster pump;
the output end of the second-stage booster pump is connected with the input end of the cartridge filter;
the output end of the cartridge filter is connected with the input end of the high-pressure pump;
the output end of the high-pressure pump is connected with the input end of the first-stage second-stage reverse osmosis filter;
the output end of the first-stage second-stage reverse osmosis filter is connected with the input end of the second-stage reverse osmosis filter through a pipeline, and an intersegmental booster pump is arranged on the pipeline;
the output end of the second-stage reverse osmosis filter and the output end of the security filter are respectively connected with the input end of the energy exchange device, and the output end of the energy exchange device is connected with the input end of the first-stage reverse osmosis filter.
Further, the first-stage reverse osmosis filter and the second-stage first-stage reverse osmosis filter both adopt membrane elements capable of tolerating 8MPa pressure, and an energy exchange device in the first-stage membrane concentration reverse osmosis system can tolerate 8MPa pressure;
the first-stage second-stage reverse osmosis filter and the second-stage reverse osmosis filter are both membrane elements capable of tolerating 12MPa pressure, and an energy exchange device in the second-stage membrane concentration reverse osmosis system can tolerate 12MPa pressure.
Further, the TDS value of the produced water obtained in the step S2 is less than or equal to 2000mg/L.
Further, in the step S31, the oxidant is hydrogen peroxide with a mass concentration of 20% -27%, and the molar ratio of the inorganic ferrous salt to the hydrogen peroxide is 2: (1.2-1.5).
Further, in step S31, the aqueous solution of inorganic ferrous salt is an aqueous solution of ferrous sulfate with a mass concentration of 18% -25%, wherein:
the molar ratio of iron ions to sulfate ions is (1.1-1.2): 1.
further, in step S31, the main component of the secondary filter cake is iron phosphate. The secondary filter cake can be used for preparing battery grade ferric phosphate after being sintered by a flash evaporation and rotary kiln.
Further, the main component of the tertiary filter cake in step S32 is ferric hydroxide.
Further, the nitrogen content of the product obtained in the step S4 is more than or equal to 20.5wt%.
The beneficial effects are that: the recycling treatment process of the aging mother liquor in the iron phosphate production process has the following beneficial effects:
1. the added value of the phosphorus recycling product is improved, namely, only ammonium dihydrogen phosphate can be recovered by the traditional process for treating the aging mother liquor in the production process of the ferric phosphate, and the market price is about 3000-5000 yuan/ton; the invention can recycle ferric phosphate, and the current market price is 15000-28000 yuan/ton;
2. the impurity is removed by the pretreatment, so that the impurity content in the iron phosphate product is further reduced;
3. through membrane concentration, the concentration of phosphate ions in the synthesis reaction is improved, so that the generated ferric phosphate particles are larger and more uniform, the quality of the product is better, and the added value of the product is further improved.
Drawings
FIG. 1 is a flow chart of a recycling treatment process of an aging mother liquor in an iron phosphate production process.
FIG. 2 is a schematic diagram of a first stage membrane concentration reverse osmosis system. Wherein:
1-a cartridge filter;
2-high pressure pump
3-section first stage reverse osmosis filter
4-inter-section booster pump
5-two-stage first stage reverse osmosis filter
6-energy exchange device
Detailed Description
The following detailed description of specific embodiments of the invention.
Example 1
A recycling treatment process of aging mother liquor in the production process of ferric phosphate comprises the following specific steps:
s1, pretreatment:
s11, introducing aging mother liquor in the production process of ferric phosphate into a raw water regulating tank;
s12, lifting the aging mother liquor in the step S11 to a high-efficiency sedimentation tank through a pump, adding a proper amount of inorganic alkali into the high-efficiency sedimentation tank while stirring, adjusting the pH value of the aging mother liquor to 8.2, continuously stirring for 45 minutes, and introducing the treated aging mother liquor into a plate-and-frame filter press, and respectively obtaining a primary filter cake and a primary filtrate after filter pressing;
s13, introducing the primary filtrate separated in the step S12 into a first reaction tank, adding a proper amount of inorganic acid aqueous solution into the first reaction tank, regulating the pH value to 5.2, and introducing the primary filtrate into a plate heat exchanger to cool to 27 ℃;
s14, introducing the primary filtrate treated in the step S13 into an ultrafiltration system to obtain ultrafiltration produced water;
s2, membrane concentration treatment:
introducing ultrafiltration produced water into a two-stage membrane concentration reverse osmosis system to obtain concentrated solution with the mass concentration of 17% and produced water, preparing pure water by the produced water through a two-stage purification reverse osmosis device again, and recycling the pure water for production, wherein:
the main components of the solute of the concentrated solution are ammonium dihydrogen phosphate and ammonium sulfate;
s3, phosphorus recovery treatment:
s31, introducing the concentrated solution obtained in the step S2 into a second reaction tank, stirring, adding an oxidant and an inorganic ferrous salt aqueous solution into the second reaction tank while adding a proper amount of inorganic alkali, regulating the pH value to 1.6, continuously stirring for 45 minutes, introducing the treated concentrated solution into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a secondary filter cake and a secondary filtrate;
s32, introducing the secondary filtrate separated in the step S31 into a third reaction tank, adding inorganic alkali into the third reaction tank while stirring, adjusting the pH value of the secondary filtrate to 5.8, continuously stirring for 40 minutes, introducing the treated secondary filtrate into a plate-and-frame filter press to perform mud-water separation, and obtaining a tertiary filter cake and a tertiary filtrate after filter pressing;
s4, evaporating and crystallizing:
and (3) introducing the tertiary filtrate obtained in the step (S32) into an MVR evaporation crystallization device, and centrifugally separating to obtain a product with the main component of ammonium sulfate.
In step S12, the inorganic base is ammonia water, and the primary filter cake mainly comprises magnesium ammonium phosphate and calcium phosphate. The primary filter cake can be sold as a calcium magnesium phosphate fertilizer product after being dried.
Further, the aqueous solution of inorganic acid in step S13 is an aqueous solution of sulfuric acid with a mass concentration of 30.
Further, the ultrafiltration system in the step S14 performs air-water combined backwashing for 1.5 minutes once every 45 minutes, and the ultrafiltration backwash water returns to the raw water regulating tank for reprocessing; and is also provided with
The ultrafiltration system was chemically cleaned every 4 months. To maintain long-term stable operation of ultrafiltration.
Further, the SDI value of the ultrafiltration product water obtained in step S14=2.6.
Further, the two-stage membrane concentration reverse osmosis system in step S2 includes a first-stage membrane concentration reverse osmosis system and a second-stage membrane concentration reverse osmosis system which are sequentially connected in series, wherein:
the first stage membrane concentration reverse osmosis system comprises:
a first stage booster pump (not shown);
the output end of the first stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage reverse osmosis filter 3;
the output end of the first-stage reverse osmosis filter 3 is connected with the input end of the second-stage first-stage reverse osmosis filter 5 through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the two-stage first-stage reverse osmosis filter 5 and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the one-stage first-stage reverse osmosis filter 3;
the second-stage membrane concentration reverse osmosis system comprises:
a second stage booster pump (not shown);
the output end of the second-stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage second-stage reverse osmosis filter;
the output end of the first-stage second-stage reverse osmosis filter is connected with the input end of the second-stage reverse osmosis filter through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the second-stage reverse osmosis filter and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the first-stage reverse osmosis filter 3.
The energy exchange device 6 is matched in the first-stage membrane concentration reverse osmosis system and the second-stage membrane concentration reverse osmosis system respectively, so that the energy of the reverse osmosis high-pressure concentrated water side flowing out of the two-stage first-stage reverse osmosis filter 5 and the two-stage second-stage reverse osmosis filter is further recovered, the flow of the reverse osmosis high-pressure pump 2 is reduced, and the electric energy is saved.
Further, the first-stage reverse osmosis filter 3 and the second-stage first-stage reverse osmosis filter 5 are both membrane elements capable of tolerating 8MPa pressure, and the energy exchange device 6 in the first-stage membrane concentration reverse osmosis system is capable of tolerating 8MPa pressure;
the first-stage second-stage reverse osmosis filter and the second-stage reverse osmosis filter both adopt membrane elements capable of tolerating 12MPa pressure, and an energy exchange device 6 in the second-stage membrane concentration reverse osmosis system can tolerate 12MPa pressure. Compared with a system without the energy exchange device 6, after the energy exchange device 6 is adopted, the flow of the high-pressure pump 2 is reduced by more than 50%, and the electric energy is saved by at least 50%.
When the anti-fouling agent is used, the anti-fouling agent and the reducing agent are added to protect a reverse osmosis membrane of the first-stage membrane concentration reverse osmosis system, no more than 50% of liquid out of the anti-fouling agent is pumped into a first-stage membrane concentration reverse osmosis membrane group of 8MPa through a high-pressure pump 2 after passing through the anti-fouling agent 1, the first-stage membrane concentration reverse osmosis module is connected in a multi-stage manner, an inter-stage booster pump 4 with an inlet pressure of 8MPa is arranged in the middle of the first-stage membrane concentration reverse osmosis module, concentrated liquid of the first-stage membrane concentration reverse osmosis enters a first-stage membrane concentration reverse osmosis concentrated pond through an energy exchange device 6 of 8MPa, the energy exchange device utilizes the high-pressure energy of concentrated water of the first-stage membrane concentration reverse osmosis to pump no less than 50% of liquid out of the other anti-fouling agent after passing through the anti-fouling agent 1 into the first-stage membrane concentration reverse osmosis membrane group of 8MPa, the flow of the high-pressure pump 2 is reduced by 50%, and the electric energy is saved by over 50%;
pumping concentrated water of a first-stage membrane concentration reverse osmosis system into a cartridge filter 1 of the second-stage membrane concentration reverse osmosis system through a second-stage booster pump, protecting a reverse osmosis membrane of the second-stage membrane concentration reverse osmosis system by adding a scale inhibitor, pumping not more than 50% of liquid out of the cartridge filter 1 into a 12MPa second-stage membrane concentration reverse osmosis membrane group through a high-pressure pump 2, connecting the second-stage membrane concentration reverse osmosis modules in a multi-stage manner, arranging an inter-stage booster pump 4 with an inlet pressure of 12MPa in the middle, enabling the concentrated liquid of the second-stage membrane concentration reverse osmosis to enter a concentrated liquid tank through an energy exchange device with the pressure of 12MPa, and pumping not less than 50% of liquid out of the second-stage membrane concentration reverse osmosis membrane group with the pressure of 12MPa after passing through the cartridge filter 1 by the energy exchange device, so that the flow of the high-pressure pump 2 is reduced by 50%, and the electric energy is saved by more than 50%; the ammonium sulfate concentration of the first-stage membrane concentrated water is concentrated from 10% to 18% by utilizing the second-stage membrane concentrated reverse osmosis. The TDS of the water produced by the second-stage membrane concentration reverse osmosis is less than or equal to 2000mg/L, the water produced by the first-stage membrane concentration and the water produced by the second-stage membrane concentration are mixed in a first-stage membrane concentration water producing pool, and the mixed water is fed into a second-stage purification reverse osmosis system to prepare pure water for recycling in a production workshop, and the concentrated water of the first-stage purification reverse osmosis is returned to the first-stage membrane concentration reverse osmosis system.
Further, the TDS value of the produced water obtained in the step S2 is less than or equal to 2000mg/L.
Further, in step S31, the oxidant is hydrogen peroxide with a mass concentration of 25%, and a molar ratio of the inorganic ferrous salt to the hydrogen peroxide is 2:1.3.
further, in step S31, the aqueous solution of inorganic ferrous salt is an aqueous solution of ferrous sulfate with a mass concentration of 18% -25%, wherein:
the molar ratio of iron ions to sulfate ions was 1.15:1.
further, in step S31, the main component of the secondary filter cake is iron phosphate. The secondary filter cake can be used for preparing battery grade ferric phosphate after being sintered by a flash evaporation and rotary kiln.
Further, the main component of the tertiary filter cake in step S32 is ferric hydroxide.
Further, the nitrogen content of the product obtained in step S4 was 20.7wt%.
Example 1 practical application case 1:
about 100 tons of aging mother liquor produced by a certain iron phosphate production factory in Hunan in daily life, wherein the total dissolved solid of the aging mother liquor is 52097mg/L, and the pH value of the aging mother liquor is 1.5, and the method comprises the following steps:
phosphate ion concentration is 38000mg/L;
the concentration of ammonium ions is 5000mg/L;
the concentration of sulfate ions is 9000mg/L;
the concentration of iron ions is 80mg/L;
the concentration of magnesium ions is 8mg/L;
the concentration of manganese ions is 8.5mg/L;
the concentration of calcium ions is 0.5mg/L.
Firstly, the factory adopts a wastewater zero-emission treatment process, namely, firstly adopts pretreatment to remove impurities, the pretreatment mainly adopts an inclined tube sedimentation tank to remove metal ions such as calcium, magnesium, manganese and iron in the wastewater by adjusting pH, then adopts membrane concentration to obtain concentrated solution, and finally carries out evaporation crystallization and salt separation to obtain ammonium sulfate and ammonium dihydrogen phosphate.
By adopting the wastewater zero-emission treatment process to treat 100 tons of the aged mother liquor, about 1.8 tons of ammonium sulfate (market price 800 yuan/ton) and 4.4 tons of ammonium dihydrogen phosphate (market price 3000 tons) can be produced, namely the total by-product has the economic benefit of 14640 yuan.
After the process described in example 1 is changed to treat 100 tons of the aged mother liquor, about 5.4 tons of ferric phosphate (market price 8000 yuan/ton) and 7 tons of ammonium sulfate (market price 800 yuan/ton) can be produced, but 13 tons of ferrous sulfate heptahydrate (market price 300 yuan/ton) and 2.5 tons of 27% hydrogen peroxide (market price 3000 yuan/ton) are needed, namely the economic benefit of the total byproducts is 37400 yuan.
The other labor costs and the running costs of the two processes are about the same, and the total cost is not taken into account, and as can be seen from the above, the treatment process of example 1 increases economic benefit by about 22760 yuan.
In addition, the ammonium sulfate, ferric phosphate and calcium magnesium phosphate fertilizer products of example 1 were identified, wherein the ammonium sulfate product meets the requirements of the standard of industrial grade ammonium sulfate (HG/T5744-2020), and the content of nitrogen (N) (on a dry basis) omega/% is 20.6%; the iron phosphate meets the requirements of iron phosphate for HG/T4701-2014 batteries, the content of Fe omega/% > is not less than 36.00, the content of P omega/% > is not less than 20.00, and the Fe/P is 0.975+/-0.005; the calcium magnesium phosphate fertilizer meets the requirement of the standard of calcium magnesium phosphate fertilizer (GB 20412-2006), the mass fraction of the effective phosphorus pentoxide is more than or equal to 15%, and the mass fraction of the water is less than or equal to 0.5%.
In summary, the recycling treatment process of the aging mother liquor in the iron phosphate production process has excellent treatment effect, compared with the original process, the industrial added value of byproducts is increased by 255.5%, and the yield of 22760 yuan is increased by treating 100 tons of aging mother liquor.
Example 2
A recycling treatment process of aging mother liquor in the production process of ferric phosphate comprises the following specific steps:
s1, pretreatment:
s11, introducing aging mother liquor in the production process of ferric phosphate into a raw water regulating tank;
s12, lifting the aging mother liquor in the step S11 to a high-efficiency sedimentation tank through a pump, adding a proper amount of inorganic alkali into the high-efficiency sedimentation tank while stirring, adjusting the pH value of the aging mother liquor to 8.0, continuously stirring for 30 minutes, and introducing the treated aging mother liquor into a plate-and-frame filter press, and respectively obtaining a primary filter cake and a primary filtrate after filter pressing;
s13, introducing the primary filtrate separated in the step S12 into a first reaction tank, adding a proper amount of inorganic acid aqueous solution into the first reaction tank, regulating the pH value to 5.0, and introducing the primary filtrate into a plate heat exchanger to cool to 25 ℃;
s14, introducing the primary filtrate treated in the step S13 into an ultrafiltration system to obtain ultrafiltration produced water;
s2, membrane concentration treatment:
introducing ultrafiltration produced water into a two-stage membrane concentration reverse osmosis system to obtain concentrated solution with the mass concentration of 16% and produced water, preparing pure water by the produced water through a two-stage purification reverse osmosis device again, and recycling the pure water for production, wherein:
the main components of the solute of the concentrated solution are ammonium dihydrogen phosphate and ammonium sulfate;
s3, phosphorus recovery treatment:
s31, introducing the concentrated solution obtained in the step S2 into a second reaction tank, stirring, adding an oxidant and an inorganic ferrous salt aqueous solution into the second reaction tank while adding a proper amount of inorganic alkali, regulating the pH value to 1.2, continuously stirring for 30 minutes, introducing the treated concentrated solution into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a secondary filter cake and a secondary filtrate;
s32, introducing the secondary filtrate separated in the step S31 into a third reaction tank, adding inorganic alkali into the third reaction tank while stirring, adjusting the pH value of the secondary filtrate to 5.5, continuously stirring for 30 minutes, introducing the treated secondary filtrate into a plate-and-frame filter press to perform mud-water separation, and obtaining a tertiary filter cake and a tertiary filtrate after filter pressing;
s4, evaporating and crystallizing:
and (3) introducing the tertiary filtrate obtained in the step (S32) into an MVR evaporation crystallization device, and centrifugally separating to obtain a product with the main component of ammonium sulfate.
Further, the total dissolved solids of the aging mother liquor during the production of iron phosphate in step S11 was 42000mg/L, and the pH was 1.2, wherein:
phosphate ion concentration is 30000mg/L;
the concentration of ammonium ions is 4000mg/L;
the concentration of sulfate ions is 8000mg/L;
iron ion concentration is 50mg/L;
the concentration of magnesium ions is 5mg/L;
the concentration of manganese ions is 5mg/L;
the concentration of calcium ions is 0mg/L.
In step S12, the inorganic base is ammonia water, and the primary filter cake mainly comprises magnesium ammonium phosphate and calcium phosphate. The primary filter cake can be sold as a calcium magnesium phosphate fertilizer product after being dried.
Further, the aqueous solution of inorganic acid in step S13 is an aqueous solution of sulfuric acid with a mass concentration of 20%.
Further, the ultrafiltration system in the step S14 performs air-water combined backwashing for 2 minutes once every 40 minutes, and the ultrafiltration backwash water returns to the raw water regulating tank for reprocessing; and is also provided with
The ultrafiltration system was chemically cleaned every 3 months. To maintain long-term stable operation of ultrafiltration.
Further, the SDI value of the ultrafiltration product water obtained in step S14=3.
Further, the two-stage membrane concentration reverse osmosis system in step S2 includes a first-stage membrane concentration reverse osmosis system and a second-stage membrane concentration reverse osmosis system which are sequentially connected in series, wherein:
the first stage membrane concentration reverse osmosis system comprises:
a first stage booster pump (not shown);
the output end of the first stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage reverse osmosis filter 3;
the output end of the first-stage reverse osmosis filter 3 is connected with the input end of the second-stage first-stage reverse osmosis filter 5 through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the two-stage first-stage reverse osmosis filter 5 and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the one-stage first-stage reverse osmosis filter 3;
the second-stage membrane concentration reverse osmosis system comprises:
a second stage booster pump (not shown);
the output end of the second-stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage second-stage reverse osmosis filter;
the output end of the first-stage second-stage reverse osmosis filter is connected with the input end of the second-stage reverse osmosis filter through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the second-stage reverse osmosis filter and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the first-stage reverse osmosis filter 3.
The energy exchange device 6 is matched in the first-stage membrane concentration reverse osmosis system and the second-stage membrane concentration reverse osmosis system respectively, so that the energy of the reverse osmosis high-pressure concentrated water side flowing out of the two-stage first-stage reverse osmosis filter 5 and the two-stage second-stage reverse osmosis filter is further recovered, the flow of the reverse osmosis high-pressure pump 2 is reduced, and the electric energy is saved.
Further, the first-stage reverse osmosis filter 3 and the second-stage first-stage reverse osmosis filter 5 are both membrane elements capable of tolerating 8MPa pressure, and the energy exchange device 6 in the first-stage membrane concentration reverse osmosis system is capable of tolerating 8MPa pressure;
the first-stage second-stage reverse osmosis filter and the second-stage reverse osmosis filter both adopt membrane elements capable of tolerating 12MPa pressure, and an energy exchange device 6 in the second-stage membrane concentration reverse osmosis system can tolerate 12MPa pressure. Compared with a system without the energy exchange device 6, after the energy exchange device 6 is adopted, the flow of the high-pressure pump 2 is reduced by more than 50%, and the electric energy is saved by at least 50%.
Further, the TDS value of the produced water obtained in the step S2 is less than or equal to 2000mg/L.
Further, in step S31, the oxidant is hydrogen peroxide with a mass concentration of 20%, and a molar ratio of the inorganic ferrous salt to the hydrogen peroxide is 2:1.2.
further, in step S31, the aqueous solution of inorganic ferrous sulfate is an aqueous solution of ferrous sulfate with a mass concentration of 18%, wherein:
the molar ratio of iron ions to sulfate ions was 1.1:1.
further, in step S31, the main component of the secondary filter cake is iron phosphate. The secondary filter cake can be used for preparing battery grade ferric phosphate after being sintered by a flash evaporation and rotary kiln.
Further, the main component of the tertiary filter cake in step S32 is ferric hydroxide.
Further, the nitrogen content of the product obtained in the step S4 is more than or equal to 20.5wt%.
Example 3
A recycling treatment process of aging mother liquor in the production process of ferric phosphate comprises the following specific steps:
s1, pretreatment:
s11, introducing aging mother liquor in the production process of ferric phosphate into a raw water regulating tank;
s12, lifting the aging mother liquor in the step S11 to a high-efficiency sedimentation tank through a pump, adding a proper amount of inorganic alkali into the high-efficiency sedimentation tank while stirring, adjusting the pH value of the aging mother liquor to 8.5, continuously stirring for 60 minutes, and introducing the treated aging mother liquor into a plate-and-frame filter press, and respectively obtaining a primary filter cake and a primary filtrate after filter pressing;
s13, introducing the primary filtrate separated in the step S12 into a first reaction tank, adding a proper amount of inorganic acid aqueous solution into the first reaction tank, regulating the pH value to 5.5, and introducing the primary filtrate into a plate heat exchanger to cool to 30 ℃;
s14, introducing the primary filtrate treated in the step S13 into an ultrafiltration system to obtain ultrafiltration produced water;
s2, membrane concentration treatment:
introducing ultrafiltration produced water into a two-stage membrane concentration reverse osmosis system to obtain concentrated solution with the mass concentration of 19% and produced water, preparing pure water by the produced water through a two-stage purification reverse osmosis device again, and recycling the pure water for production, wherein:
the main components of the solute of the concentrated solution are ammonium dihydrogen phosphate and ammonium sulfate;
s3, phosphorus recovery treatment:
s31, introducing the concentrated solution obtained in the step S2 into a second reaction tank, stirring, adding an oxidant and an inorganic ferrous salt aqueous solution into the second reaction tank while adding a proper amount of inorganic alkali, regulating the pH value to 2.0, continuously stirring for 60 minutes, introducing the treated concentrated solution into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a secondary filter cake and a secondary filtrate;
s32, introducing the secondary filtrate separated in the step S31 into a third reaction tank, adding inorganic alkali into the third reaction tank while stirring, adjusting the pH value of the secondary filtrate to 6.0, continuously stirring for 60 minutes, introducing the treated secondary filtrate into a plate-and-frame filter press to perform mud-water separation, and obtaining a tertiary filter cake and a tertiary filtrate after filter pressing;
s4, evaporating and crystallizing:
and (3) introducing the tertiary filtrate obtained in the step (S32) into an MVR evaporation crystallization device, and centrifugally separating to obtain a product with the main component of ammonium sulfate.
Further, the total dissolved solids of the aging mother liquor during the iron phosphate production in step S11 was 56000mg/L, and the pH thereof was 2.0, wherein:
phosphate ion concentration is 40000mg/L;
the concentration of ammonium ions is 6000mg/L;
the concentration of sulfate ions is 10000mg/L;
the concentration of iron ions is 100mg/L;
the concentration of magnesium ions is 10mg/L;
the concentration of manganese ions is 10mg/L;
the concentration of calcium ions is 1mg/L.
In step S12, the inorganic base is ammonia water, and the primary filter cake mainly comprises magnesium ammonium phosphate and calcium phosphate. The primary filter cake can be sold as a calcium magnesium phosphate fertilizer product after being dried.
Further, the aqueous solution of inorganic acid in step S13 is an aqueous solution of sulfuric acid with a mass concentration of 98%.
Further, the ultrafiltration system in the step S14 performs air-water combined backwashing for 1 minute every 50 minutes, and the ultrafiltration backwash water returns to the raw water regulating tank for reprocessing; and is also provided with
The ultrafiltration system was chemically cleaned every 6 months. To maintain long-term stable operation of ultrafiltration.
Further, the SDI value of the ultrafiltration produced water obtained in the step S14 is less than or equal to 3.
Further, the two-stage membrane concentration reverse osmosis system in step S2 includes a first-stage membrane concentration reverse osmosis system and a second-stage membrane concentration reverse osmosis system which are sequentially connected in series, wherein:
the first stage membrane concentration reverse osmosis system comprises:
a first stage booster pump (not shown);
the output end of the first stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage reverse osmosis filter 3;
the output end of the first-stage reverse osmosis filter 3 is connected with the input end of the second-stage first-stage reverse osmosis filter 5 through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the two-stage first-stage reverse osmosis filter 5 and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the one-stage first-stage reverse osmosis filter 3;
the second-stage membrane concentration reverse osmosis system comprises:
a second stage booster pump (not shown);
the output end of the second-stage booster pump is connected with the input end of the cartridge filter 1;
the output end of the cartridge filter 1 is connected with the input end of the high-pressure pump 2;
the output end of the high-pressure pump 2 is connected with the input end of the first-stage second-stage reverse osmosis filter;
the output end of the first-stage second-stage reverse osmosis filter is connected with the input end of the second-stage reverse osmosis filter through a pipeline, and an inter-stage booster pump 4 is arranged on the pipeline;
the output end of the second-stage reverse osmosis filter and the output end of the cartridge filter 1 are respectively connected with the input end of the energy exchange device 6, and the output end of the energy exchange device 6 is connected with the input end of the first-stage reverse osmosis filter 3.
The energy exchange device 6 is matched in the first-stage membrane concentration reverse osmosis system and the second-stage membrane concentration reverse osmosis system respectively, so that the energy of the reverse osmosis high-pressure concentrated water side flowing out of the two-stage first-stage reverse osmosis filter 5 and the two-stage second-stage reverse osmosis filter is further recovered, the flow of the reverse osmosis high-pressure pump 2 is reduced, and the electric energy is saved.
Further, the first-stage reverse osmosis filter 3 and the second-stage first-stage reverse osmosis filter 5 are both membrane elements capable of tolerating 8MPa pressure, and the energy exchange device 6 in the first-stage membrane concentration reverse osmosis system is capable of tolerating 8MPa pressure;
the first-stage second-stage reverse osmosis filter and the second-stage reverse osmosis filter both adopt membrane elements capable of tolerating 12MPa pressure, and an energy exchange device 6 in the second-stage membrane concentration reverse osmosis system can tolerate 12MPa pressure. Compared with a system without the energy exchange device 6, after the energy exchange device 6 is adopted, the flow of the high-pressure pump 2 is reduced by more than 50%, and the electric energy is saved by at least 50%.
Further, the TDS value of the produced water obtained in the step S2 is less than or equal to 2000mg/L.
Further, in the step S31, the oxidant is hydrogen peroxide with a mass concentration of 20% -27%, and the molar ratio of the inorganic ferrous salt to the hydrogen peroxide is 2:1.5.
further, in step S31, the aqueous solution of inorganic ferrous salt is an aqueous solution of ferrous sulfate with a mass concentration of 18% -25%, wherein:
the molar ratio of iron ions to sulfate ions was 1.2:1.
further, in step S31, the main component of the secondary filter cake is iron phosphate. The secondary filter cake can be used for preparing battery grade ferric phosphate after being sintered by a flash evaporation and rotary kiln.
Further, the main component of the tertiary filter cake in step S32 is ferric hydroxide.
Further, the nitrogen content of the product obtained in the step S4 is more than or equal to 20.5wt%.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (4)
1. A recycling treatment process of aging mother liquor in the production process of ferric phosphate is characterized by comprising the following specific steps:
s1, pretreatment:
s11, introducing aging mother liquor in the production process of ferric phosphate into a raw water regulating tank;
s12, lifting the aging mother liquor in the step S11 to a high-efficiency sedimentation tank through a pump, adding a proper amount of inorganic alkali into the high-efficiency sedimentation tank while stirring, adjusting the pH value of the aging mother liquor to 8.0-8.5, continuously stirring for at least 30 minutes, and introducing the treated aging mother liquor into a plate-and-frame filter press, and respectively obtaining a primary filter cake and a primary filtrate after filter pressing;
s13, introducing the primary filtrate separated in the step S12 into a first reaction tank, then adding a proper amount of inorganic acid aqueous solution into the first reaction tank, regulating the pH value to 5.0-5.5, and then introducing the primary filtrate into a plate heat exchanger to cool to 25-30 ℃;
s14, introducing the primary filtrate treated in the step S13 into an ultrafiltration system to obtain ultrafiltration produced water;
s2, membrane concentration treatment:
introducing ultrafiltration produced water into a two-stage membrane concentration reverse osmosis system to obtain concentrated solution with the mass concentration of 16% -19% and produced water, preparing pure water by the produced water through a two-stage purification reverse osmosis device again, and recycling the pure water for production, wherein:
the main components of the solute of the concentrated solution are ammonium dihydrogen phosphate and ammonium sulfate;
s3, phosphorus recovery treatment:
s31, introducing the concentrated solution obtained in the step S2 into a second reaction tank, stirring, adding an oxidant and an inorganic ferrous salt aqueous solution into the second reaction tank while adding a proper amount of inorganic alkali, regulating the pH value to 1.2-2.0, continuously stirring for at least 30 minutes, and introducing the treated concentrated solution into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a secondary filter cake and a secondary filtrate;
s32, introducing the secondary filtrate separated in the step S31 into a third reaction tank, adding inorganic alkali into the third reaction tank while stirring, adjusting the pH value of the secondary filtrate to 5.5-6.0, continuously stirring for at least 30 minutes, introducing the treated secondary filtrate into a plate-and-frame filter press to perform mud-water separation, and performing filter pressing to obtain a tertiary filter cake and a tertiary filtrate;
s4, evaporating and crystallizing:
introducing the tertiary filtrate obtained in the step S32 into an MVR evaporation crystallization device, and centrifugally separating to obtain a product with the main component of ammonium sulfate, wherein:
the total dissolved solids of the aging mother liquor in the production process of the ferric phosphate in the step S11 is 42000-56000 mg/L, and the pH value is 1.2-2.0, wherein:
the concentration of phosphate radical ion is 30000-40000 mg/L;
the concentration of ammonium ions is 4000-6000 mg/L;
the concentration of sulfate ions is 8000-10000 mg/L;
the concentration of iron ions is 50-100 mg/L;
the concentration of magnesium ions is 5-10 mg/L;
the concentration of manganese ions is 5-10 mg/L;
the concentration of calcium ions is 0-1 mg/L;
the SDI value of the ultrafiltration produced water obtained in the step S14 is less than or equal to 3;
in the step S31, the oxidant is hydrogen peroxide with the mass concentration of 20% -27%, and the molar ratio of the inorganic ferrous salt to the hydrogen peroxide is 2: (1.2-1.5);
the inorganic ferrous salt aqueous solution in the step S31 is ferrous sulfate aqueous solution with the mass concentration of 18-25%, wherein:
the molar ratio of iron ions to sulfate ions is (1.1-1.2): 1, a step of;
the two-stage membrane concentration reverse osmosis system in the step S2 comprises a first-stage membrane concentration reverse osmosis system and a second-stage membrane concentration reverse osmosis system which are sequentially connected in series, wherein:
the first stage membrane concentration reverse osmosis system comprises:
a first stage booster pump;
the output end of the first stage booster pump is connected with the input end of the cartridge filter;
the output end of the cartridge filter is connected with the input end of the high-pressure pump;
the output end of the high-pressure pump is connected with the input end of the first-stage reverse osmosis filter;
the output end of the first-stage reverse osmosis filter is connected with the input end of the second-stage first-stage reverse osmosis filter through a pipeline, and an intersegmental booster pump is arranged on the pipeline;
the output end of the two sections of the first-stage reverse osmosis filters and the output end of the security filter are respectively connected with the input end of the energy exchange device, and the output end of the energy exchange device is connected with the input end of the first section of the first-stage reverse osmosis filter;
the second-stage membrane concentration reverse osmosis system comprises:
a second stage booster pump;
the output end of the second-stage booster pump is connected with the input end of the cartridge filter;
the output end of the cartridge filter is connected with the input end of the high-pressure pump;
the output end of the high-pressure pump is connected with the input end of the first-stage second-stage reverse osmosis filter;
the output end of the first-stage second-stage reverse osmosis filter is connected with the input end of the second-stage reverse osmosis filter through a pipeline, and an intersegmental booster pump is arranged on the pipeline;
the output end of the second-stage reverse osmosis filter and the output end of the security filter are respectively connected with the input end of the energy exchange device, and the output end of the energy exchange device is connected with the input end of the first-stage reverse osmosis filter;
the first-stage reverse osmosis filter and the second-stage first-stage reverse osmosis filter both adopt membrane elements capable of tolerating 8MPa pressure, and an energy exchange device in the first-stage membrane concentration reverse osmosis system can tolerate 8MPa pressure;
the first-stage second-stage reverse osmosis filter and the second-stage reverse osmosis filter are both membrane elements capable of tolerating 12MPa pressure, and an energy exchange device in the second-stage membrane concentration reverse osmosis system can tolerate 12MPa pressure.
2. The recycling treatment process of aging mother liquor in the iron phosphate production process according to claim 1, wherein the inorganic base in the step S12 is ammonia water, the primary filter cake mainly comprises magnesium ammonium phosphate and calcium phosphate, and the inorganic acid aqueous solution in the step S13 is sulfuric acid aqueous solution with the mass concentration of 20% -98%.
3. The recycling treatment process of aging mother liquor in the iron phosphate production process according to claim 1, wherein the TDS value of produced water obtained in the step S2 is less than or equal to 2000mg/L.
4. The recycling treatment process of aging mother liquor in the iron phosphate production process according to claim 1, wherein the main component of the secondary filter cake in the step S31 is iron phosphate, the main component of the tertiary filter cake in the step S32 is iron hydroxide, and the nitrogen content of the product obtained in the step S4 is more than or equal to 20.5wt%.
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