CN114605018A - Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recycling salt - Google Patents
Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recycling salt Download PDFInfo
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- CN114605018A CN114605018A CN202210115130.4A CN202210115130A CN114605018A CN 114605018 A CN114605018 A CN 114605018A CN 202210115130 A CN202210115130 A CN 202210115130A CN 114605018 A CN114605018 A CN 114605018A
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- 238000000034 method Methods 0.000 title claims abstract description 64
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 59
- 239000011574 phosphorus Substances 0.000 title claims abstract description 59
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 55
- 239000011737 fluorine Substances 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- 150000003839 salts Chemical class 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims description 9
- 239000013505 freshwater Substances 0.000 claims abstract description 116
- 238000001179 sorption measurement Methods 0.000 claims abstract description 80
- 238000001704 evaporation Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000008020 evaporation Effects 0.000 claims abstract description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims description 144
- 239000012266 salt solution Substances 0.000 claims description 92
- 239000003463 adsorbent Substances 0.000 claims description 84
- 239000007790 solid phase Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 238000000926 separation method Methods 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 12
- 239000003957 anion exchange resin Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005191 phase separation Methods 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Inorganic Chemistry (AREA)
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Abstract
The invention provides a method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt. Firstly, separating the wastewater into a concentrated water phase and a fresh water phase through flash evaporation phase splitting and separating out solids, and then treating the concentrated water phase, the fresh water phase and the separated out solids to realize the purpose of obtaining an industrially recyclable sodium chloride product on the basis of removing phosphorus and fluorine impurities and reducing the TOC content; the steps of flash evaporation phase splitting, melting, dissolving, insoluble substance conversion, adsorption and the like selected by the method have the characteristics of simple and convenient operation, simple equipment, easy maintenance, convenient popularization and application, low cost and good economy.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt.
Background
The phosphorus-containing fluorine-containing high-salt organic wastewater mainly comes from production processes of pesticides, phosphate fertilizers and the like, has high sodium chloride content, complex organic pollutant composition and high Total Organic Carbon (TOC) content, and particularly contains impurity phosphorus and impurity fluorine which are difficult to remove; therefore, the treatment difficulty of the phosphorus-containing fluorine-containing high-salt organic wastewater is high, and environmental pollution is caused; in addition, because the impurities of phosphorus, fluorine and TOC are difficult to completely remove, the quality of sodium chloride recovered from the wastewater is low, and the sodium chloride cannot be effectively utilized, thereby causing resource waste.
In the prior art, high-salt industrial wastewater containing phosphorus is evaporated and concentrated to obtain an inorganic salt crude product, the inorganic salt crude product needs to be washed by a special washing solution to remove phosphorus in the inorganic salt crude product, and the washed inorganic salt crude product needs to be contacted with oxygen-containing gas at a high temperature to be carbonized to obtain high-purity inorganic salt.
In the prior art, the wastewater is introduced into a filter, a reverse osmosis membrane device and a special reactor for treatment, and a proper amount of magnesium salt, MgO, phosphate and other substances are added into the special reactor to obtain agricultural fertilizer and medium-concentration water. The medium concentrated water also needs to be further and more complicated treated, namely the medium concentrated water is introduced into a graphene adsorption tower for adsorption and filtration to remove organic matters such as oil stains and the like; introducing the deoiled medium-concentration water into an evaporator to obtain crystallized solid powder and mixed gas; introducing the mixed gas into a gas membrane separator for separation to obtain pure water and thickened mixed gas; introducing the thickened mixed gas into a condenser for condensation treatment to obtain water and non-condensable gas; introducing the non-condensable gas into a microwave ultraviolet catalytic reactor to decompose to obtain CO and HO.
In the prior art, the method also comprises a series of complex processes of dissolution, multi-connection reaction, tubular membrane system treatment, water quality adjustment (acid regulation), activated carbon adsorption, fluoride ion adsorption, ammonia nitrogen adsorption, nanofiltration treatment, chelate resin adsorption, evaporative crystallization and the like.
In the prior art, evaporative crystallization is also adopted to divide high-salinity wastewater into a fresh water phase and a salt-containing solid phase, but when the wastewater contains organic matters, the fresh water phase contains impurities due to factors such as entrainment and the like, and the quality of the fresh water needs to be further improved by a biological method and other modes, for example, a biological treatment area is arranged for removing the organic matters from condensate formed after evaporation in the high-salinity organic wastewater; and a large amount of organic impurities remain in the solid phase containing salt, so that the solid phase is still dangerous waste. Although the solid phase containing salt can reduce the Total Organic Carbon (TOC) content by burning and the like, in view of introducing phosphorus and fluorine impurities in the production process of pesticides, phosphate fertilizers and the like, the impurities still remain in the solid phase after burning, so that the quality of the recovered sodium chloride is poor and the recovered sodium chloride cannot be reused industrially. For the impurity-containing waste salt, precipitating and removing impurities from a salt solution by adding a precipitator, a flocculating agent and the like, for example, adding calcium chloride into glyphosate production wastewater to partially remove impurity phosphorus; adding a complexing agent consisting of polyaluminium sulfate, polyferric sulfate, zirconium oxide, active titanium dioxide, water and a fixing agent into the coal chemical industry production wastewater to remove fluorine; the technical scheme is that a compound flocculating agent consisting of hydrogen peroxide, polyaluminium chloride, inorganic aluminum salt and inorganic cerium salt is added into the electroplating wastewater, and impurities of phosphorus and fluorine in the wastewater are removed at the same time. However, the impurity removal effect of precipitation or flocculation is limited and new impurities are introduced due to the addition of a precipitating agent or a flocculating agent, making it difficult to ensure the quality of the recovered salt. Although the membrane separation method can remove impurities in high-salinity water without introducing secondary pollution, such as trapping inorganic phosphorus and organic phosphorus in saline wastewater by using a nanofiltration membrane, the method has high equipment cost and is accompanied with membrane pollution and other problems.
Therefore, at present, there is no integrated treatment mode for the phosphorus-containing and fluorine-containing high-salt organic wastewater, and the existing technologies such as biological method, incineration method, chemical precipitation method, membrane separation method and the like can partially achieve the purpose of reducing the content of organic matters or removing impurity phosphorus and impurity fluorine, but are still limited by the limitations of limited treatment capacity, incomplete impurity removal, introduction of secondary pollution, overhigh cost and the like.
Disclosure of Invention
The invention aims to provide a method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt, which is characterized by comprising the following steps:
(1) carrying out flash evaporation phase separation on the phosphorus-containing fluorine-containing high-salt organic wastewater to form a concentrated water phase and a light water phase, and after a solid phase is separated out, carrying out treatment according to the steps (2) to (4) which are not in sequence; wherein, the liquid which is not evaporated in the flash evaporation process is a concentrated water phase, and the steam collected by condensation is a fresh water phase;
(2) the solid phase precipitated in the flash evaporation process is treated according to the steps (2.1) to (2.7):
(2.1) solid phase melting:
melting the solid phase;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1), and preparing a salt solution with water;
(2.3) insoluble matter conversion
Adding insoluble substance conversion medicament calcium carbonate into the salt solution in the step (2.2), fully treating, and performing solid-liquid separation;
(2.4) first-order adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), and carrying out solid-liquid separation after full treatment;
(2.5) Secondary adsorption
An adsorption bed layer is formed by a salt solution secondary adsorbent, and the salt solution is collected after the liquid separated in the step (2.4) passes through the adsorption bed layer;
(2.6) evaporative crystallization
And (3) evaporating and crystallizing the salt solution collected in the step (2.5), wherein a crystallization solid phase is recovered sodium chloride.
(3) The light water phase separated out in the flash evaporation process needs to be treated according to the steps (3.1) - (3.2):
(3.1) primary adsorption of a fresh water phase:
adding a fresh water phase primary adsorbent into the fresh water phase collected in the step (1), fully treating, and performing solid-liquid separation;
(3.2) fresh-water phase two-stage adsorption
And (3) forming an adsorption bed layer by using a fresh water phase secondary adsorbent, and carrying out solid-liquid separation after the fresh water phase treated in the step (3.1) passes through the adsorption bed layer to obtain the treated fresh water phase.
(4) Mixing the non-evaporated concentrated aqueous phase with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater in the flash evaporation process, and then carrying out flash evaporation phase splitting according to the method (1).
Further, in the step (1), the flash evaporation phase separation is as follows: preheating the phosphorus-containing and fluorine-containing high-salt organic wastewater to 95-105 ℃, setting the flash pressure to be 55-70 Kpa, and performing flash evaporation phase separation to form a concentrated water phase and a fresh water phase and separate out a solid phase.
Further, in the step (1): the water quality of the phosphorus-containing fluorine-containing high-salt organic wastewater is characterized in that the pH value is 6-9, the mass fraction of sodium chloride is 15-30%, the TOC content is 5000-9000 mg/L, the total phosphorus content is 300-650 mg/L, and the fluorine content is 300-500 mg/L.
Further, in the step (2): preferably, step (2.1) is a melt treatment at a temperature ranging from 900 ℃ to 1000 ℃ for 8 minutes to 15 minutes; preferably, in the step (2.2), the molten solid phase treated in the step (2.1) is firstly cooled to the temperature of 100-200 ℃, and then a salt solution is prepared according to the mass ratio of the cooled solid phase to distilled water of 1: 3-1: 5; preferably, in the step (2.3), 10g to 50g of insoluble substance conversion medicament is added into each liter of salt solution, and the mixture is stirred for 20 minutes to 60 minutes at the speed of 10rpm (revolutions per minute) to 150rpm in the temperature range of 50 ℃ to 90 ℃; preferably, in the step (2.4), 20g to 100g of the salt solution primary adsorbent is added into the liquid separated in the step (2.3), and the mixture is stirred for 20 minutes to 60 minutes at the speed of 10rpm to 150rpm within the temperature range of 40 ℃ to 70 ℃; preferably, in the step (2.5), an adsorption bed layer with the height of 15-45 cm is formed by the salt solution secondary adsorbent, the temperature of the salt solution is kept at 40-70 ℃, the salt solution passes through the adsorption bed layer at the speed of 1BV/h (bed volume/hour) to 5BV/h, the salt solution secondary adsorbent in unit volume needs to process 20-40 times volume of salt solution, and the salt solution passing through the adsorption bed layer and the salt solution secondary adsorbent completing secondary adsorption are respectively collected; preferably, in the step (2.6), the salt solution is subjected to evaporative crystallization, the crystalline solid phase is recovered sodium chloride, and the distilled water obtained by evaporative condensation is reused in the step (2.2);
further, in the step (2): preferably, the insoluble substance conversion chemical in the step (2.3) is light calcium carbonate with 200 meshes to 800 meshes; preferably, the salt solution primary adsorbent in the step (2.4) is granular activated carbon with 10 meshes to 80 meshes; preferably, the salt solution secondary adsorbent in the step (2.5) is D201 type macroporous strongly basic styrene anion exchange resin;
further, the distilled water used for dissolving in the step (2.2) is obtained from the distilled water condensed and recovered in the evaporation and crystallization process in the step (2.6) and the distilled water supplemented externally; the sodium chloride collected by the evaporation and crystallization in the step (2.6) can be used for industrial application, and the distilled water obtained by evaporation and condensation can be reused in the step (2.2).
Further, the insoluble matter converting chemical in the step (2.3) is recycled for 20 to 30 times after solid-liquid separation.
Further, in the step (3): preferably, in the step (3.1), 20g to 100g of the fresh water phase primary adsorbent is added into each liter of the fresh water phase, the mixture is stirred for 20 minutes to 60 minutes at the temperature of 40 ℃ to 70 ℃ at the speed of 10rpm to 150rpm, and the fresh water phase primary adsorbent are separated and collected; preferably, in the step (3.2), an adsorption bed layer with the height of 15-45 cm is formed by the fresh water phase secondary adsorbent, the temperature of the fresh water phase is kept at 40-70 ℃, the fresh water phase is made to pass through the adsorption bed layer at the speed of 1BV/h (bed volume/hour) to 5BV/h, the fresh water phase secondary adsorbent in unit volume needs to process 20-40 times volume of fresh water phase, the impurity removal is completed through the fresh water phase of the adsorption bed layer, the fresh water phase secondary adsorbent can be discharged or used for other purposes, and the fresh water phase secondary adsorbent is collected.
Further, the fresh water phase primary adsorbent in the step (3.1) is granular activated carbon; the fresh water phase secondary adsorbent in the step (3.2) is D201 type macroporous strongly basic styrene anion exchange resin.
Further, the fresh water phase primary adsorbent in the step (3.1) is a salt solution primary adsorbent which is not treated after the step (2.4) is completed; after the step (3.1) is completed, the fresh water phase first-stage adsorbent can be regenerated and recycled by adopting methods such as thermal regeneration and the like;
further, the fresh water phase secondary adsorbent in the step (3.2) is an untreated salt solution secondary adsorbent after the step (2.4) is completed; after the step (3.2) is completed, the fresh water phase secondary adsorbent can be regenerated and recycled by adopting methods of firstly alkali washing and then water washing and the like.
After the technical scheme is adopted, the invention mainly has the following effects:
1. by adopting the method, the phosphorus and fluorine removal with high removal rate can be realized simultaneously on the premise of not introducing new impurities, and the contents of phosphorus, fluorine and TOC in the salt solution can be further reduced.
2. Simple operation, simple equipment, easy maintenance and convenient popularization and application. The steps of flash evaporation phase splitting, solid phase melting, dissolving, insoluble substance conversion, primary adsorption, secondary adsorption and evaporative crystallization of the salt solution and the fresh water phase, which are related in the method, have lower requirements on operation and equipment, are easy to maintain and are convenient to popularize.
3. Low cost and good economical efficiency. The insoluble substance conversion medicament and the adsorbent adopted by the method are easy to obtain, have low price, can be recycled, gradient utilized and regenerated for multiple times, and can save material consumption and reduce the cost of wastewater treatment and salt recovery compared with the prior art.
4. Fully recycling resources and being beneficial to environmental protection. The method comprises the steps of firstly, separating the phosphorus-containing and fluorine-containing high-salt organic wastewater into a concentrated water phase and a fresh water phase in a flash evaporation phase-splitting manner and separating out a solid phase; mixing the concentrated aqueous phase still comprising the phosphorus-containing fluorine-containing high-salt organic wastewater with the wastewater of the next batch, and then carrying out flash evaporation phase splitting again to ensure that the wastewater is not discharged; the TOC content in the fresh water phase obtained by flash evaporation phase splitting is effectively reduced after the fresh water phase is subjected to two steps of fresh water phase primary adsorption and fresh water phase secondary adsorption, so that the aim of being beneficial to environmental protection is fulfilled; and (3) the solid phase separated out by flash evaporation and phase splitting is subjected to solid phase melting, dissolution, insoluble substance conversion, primary absorption of a salt solution, secondary absorption of the salt solution, evaporative crystallization and other steps in sequence, and then high-quality sodium chloride is recovered, so that the aim of fully recovering resources is fulfilled.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a method for treating high-salt organic wastewater containing phosphorus and fluorine and recovering salt is characterized by comprising the following steps:
(1) in the embodiment, phosphorus-containing and fluorine-containing high-salt organic wastewater is used as an experimental object, and the water quality is characterized in that the pH is 6.2, the mass fraction of sodium chloride is 21.64%, the average value of the TOC content is 8455mg/L, the total phosphorus content is 628.2mg/L, and the fluorine content is 330.4 mg/L.
Preheating the phosphorus-containing and fluorine-containing high-salt organic wastewater to 100 ℃, setting the flash evaporation pressure to be 60Kpa, and performing flash evaporation phase separation to form a concentrated water phase and a fresh water phase and separate out a solid phase.
Processing according to the steps (2) to (4) which are not in sequence; it is worth noting that the liquid that is not evaporated in the flash evaporation process is a concentrated aqueous phase, and the vapor collected by condensation is a dilute aqueous phase;
(2) the solid phase precipitated in the flash evaporation process is treated according to the steps (2.1) to (2.7):
(2.1) solid phase melting:
melting the solid phase; step (2.1) is a melt treatment at 1000 ℃ for 8 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 150 ℃, and then mixing the molten solid phase with the distilled water phase according to the mass ratio of the solid phase to the distilled water phase of 1: 4 preparing a salt solution according to the proportion;
(2.3) insoluble matter conversion
Adding an insoluble substance conversion medicament into the salt solution obtained in the step (2.2), fully treating, namely adding 30g of 600-mesh light calcium carbonate serving as the insoluble substance conversion medicament into each liter of salt solution, stirring at the temperature of 70 ℃ at the speed of 80rmp for 40 minutes, and then carrying out solid-liquid separation;
the insoluble substance conversion agent can be recycled for 25 times after solid-liquid separation.
(2.4) first-order adsorption
And (3) adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular activated carbon with the granularity of 46-60 meshes as the salt solution primary adsorbent, adding 60g of activated carbon into each liter of salt solution, stirring for 40 minutes at the temperature of 55 ℃ at the speed of 80rmp, and then carrying out solid-liquid separation on the salt solution and the used salt solution primary adsorbent.
(2.5) Secondary adsorption
An adsorption bed layer is formed by a salt solution secondary adsorbent, and the salt solution is collected after the liquid separated in the step (2.4) passes through the adsorption bed layer; the macroporous strongly basic styrene anion exchange resin with the model number D201 is used as a secondary adsorbent of a salt solution and is filled into a column to form an adsorption bed layer with the height of 30cm, the dosage of the secondary adsorbent of the salt solution is 1/30 of the volume of the salt solution collected after the step (2.4) is completed, the temperature of the salt solution is kept at 55 ℃, the salt solution passes through the adsorption bed layer at the speed of 3BV/h, and the salt solution which continuously flows out and the resin which completes the secondary adsorption of the salt solution are respectively collected.
(2.6) evaporative crystallization
And (3) evaporating and crystallizing the salt solution collected in the step (2.5), wherein a crystallization solid phase is recovered sodium chloride. In the step (2.6), the salt solution is evaporated and crystallized, the crystallized solid phase is recovered sodium chloride, and the distilled water obtained by evaporation and condensation is reused in the step (2.2).
(3) The light water phase separated out in the flash evaporation process needs to be treated according to the steps (3.1) - (3.2):
(3.1) primary adsorption of a fresh water phase:
and (2) adding a fresh water phase primary adsorbent (the activated carbon used in the step (2.4)) into the fresh water phase collected in the step (1), fully treating, namely adding 60g of activated carbon into each liter of fresh water phase, stirring for 40 minutes at the temperature of 55 ℃ at the speed of 80rmp, and then carrying out solid-liquid separation on the fresh water phase and the fresh water phase primary adsorbent.
(3.2) fresh-water phase two-stage adsorption
And (3) forming an adsorption bed layer by using a fresh water phase secondary adsorbent (the adsorbent used in the step (2.5)), and carrying out solid-liquid separation after the fresh water phase treated in the step (3.1) passes through the adsorption bed layer. The used macroporous strongly basic styrene anion exchange resin of D201 is used as a fresh water phase secondary adsorbent, the fresh water phase secondary adsorbent is filled into a column to form an adsorption bed layer with the height of 30cm, the using amount of the fresh water phase secondary adsorbent is 1/25 of the volume of a fresh water phase to be treated, the temperature of the fresh water phase is kept at 55 ℃, the fresh water phase is enabled to pass through the adsorption bed layer at the speed of 3BV/h, and the continuously flowing fresh water phase and the resin for completing the fresh water phase secondary adsorption are respectively collected.
(4) Mixing the non-evaporated concentrated aqueous phase with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater in the flash evaporation process, and then carrying out flash evaporation phase splitting according to the method (1).
Example 2:
a method for treating high-salt organic wastewater containing phosphorus and fluorine and recovering salt is characterized by comprising the following steps:
(1) in the embodiment, phosphorus-containing and fluorine-containing high-salt organic wastewater is used as an experimental object, and the water quality is characterized in that the pH is 7.3, the mass fraction of sodium chloride is 28.52%, the average value of the TOC content is 6246.5mg/L, the total phosphorus content is 434.1mg/L, and the fluorine content is 378 mg/L.
Preheating the phosphorus-containing and fluorine-containing high-salt organic wastewater to 95 ℃, setting the flash pressure to be 55Kpa, and performing flash evaporation phase separation to form a concentrated water phase and a fresh water phase and separate out a solid phase.
Processing according to the steps (2) to (4) which are not in sequence; it is worth noting that the liquid that is not evaporated in the flash evaporation process is a concentrated aqueous phase, and the vapor collected by condensation is a dilute aqueous phase;
(2) the solid phase precipitated in the flash evaporation process is treated according to the steps (2.1) to (2.7):
(2.1) solid phase melting:
melting the solid phase; step (2.1) is a melt treatment at 900 ℃ for 15 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 200 ℃, and then mixing the molten solid phase with the distilled water phase according to the mass ratio of the solid phase to the distilled water phase of 1:5 preparing a salt solution;
(2.3) insoluble matter conversion
Adding an insoluble substance conversion medicament into the salt solution obtained in the step (2.2), fully treating, namely adding 10g of 800-mesh light calcium carbonate serving as the insoluble substance conversion medicament into each liter of salt solution, stirring for 20 minutes at the temperature of 90 ℃ at the speed of 150rmp, and then carrying out solid-liquid separation;
the insoluble substance conversion agent can be recycled for 20 times after solid-liquid separation.
(2.4) first-order adsorption
And (3) adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular activated carbon with the granularity of 60-80 meshes as the salt solution primary adsorbent, adding 20g of activated carbon into each liter of salt solution, stirring for 20 minutes at the temperature of 70 ℃ at the speed of 150rmp, and then carrying out solid-liquid separation on the salt solution and the used salt solution primary adsorbent.
(2.5) Secondary adsorption
An adsorption bed layer is formed by a salt solution secondary adsorbent, and the salt solution is collected after the liquid separated in the step (2.4) passes through the adsorption bed layer; the macroporous strongly basic styrene anion exchange resin with the model number D201 is used as a secondary adsorbent of a salt solution and is filled into a column to form an adsorption bed layer with the height of 45cm, the dosage of the secondary adsorbent of the salt solution is 1/22 of the volume of the salt solution collected after the step (2.4) is completed, the temperature of the salt solution is kept at 70 ℃, the salt solution passes through the adsorption bed layer at the speed of 5BV/h, and the salt solution which continuously flows out and the resin which completes the secondary adsorption of the salt solution are respectively collected.
(2.6) evaporative crystallization
And (3) evaporating and crystallizing the salt solution collected in the step (2.5), wherein a crystallization solid phase is recovered sodium chloride. The distilled water obtained by evaporation and condensation is reused in the step (2.2).
(3) The light water phase separated out in the flash evaporation process needs to be treated according to the steps (3.1) - (3.2):
(3.1) primary adsorption of a fresh water phase:
and (2) adding a fresh water phase primary adsorbent (the activated carbon used in the step (2.4)) into the fresh water phase collected in the step (1), fully treating, namely adding 20g of activated carbon into each liter of fresh water phase, stirring for 20 minutes at the temperature of 70 ℃ at the speed of 150rmp, and then carrying out solid-liquid separation on the fresh water phase and the fresh water phase primary adsorbent.
(3.2) fresh-water phase two-stage adsorption
And (3) forming an adsorption bed layer by using a fresh water phase secondary adsorbent (the adsorbent used in the step (2.5)), and carrying out solid-liquid separation after the fresh water phase treated in the step (3.1) passes through the adsorption bed layer. The used D201 macroporous strongly basic styrene anion exchange resin is used as a fresh water phase secondary adsorbent, the adsorbent is filled into a column to form an adsorption bed layer with the height of 45cm, the dosage of the fresh water phase secondary adsorbent is 1/20 of the volume of the fresh water phase to be treated, the temperature of the fresh water phase is kept at 70 ℃, the fresh water phase is enabled to pass through the adsorption bed layer at the speed of 5BV/h, and the continuously flowing fresh water phase and the resin for completing the fresh water phase secondary adsorption are respectively collected.
(4) Mixing the non-evaporated concentrated aqueous phase with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater in the flash evaporation process, and then carrying out flash evaporation phase splitting according to the method (1).
Example 3:
a method for treating high-salt organic wastewater containing phosphorus and fluorine and recovering salt is characterized by comprising the following steps:
(1) in the embodiment, phosphorus-containing and fluorine-containing high-salt organic wastewater is used as an experimental object, and the water quality is characterized in that the pH is 8.8, the mass fraction of sodium chloride is 17.76%, the TOC content is 5639mg/L, the total phosphorus content is 330.8mg/L, and the fluorine content is 476.7 mg/L.
Preheating the phosphorus-containing fluorine-containing high-salt organic wastewater to 105 ℃, setting the flash evaporation pressure to be 70Kpa, and performing flash evaporation phase separation to form a concentrated water phase and a fresh water phase and separate out a solid phase.
Processing according to the steps (2) to (4) which are not in sequence; it is worth noting that the liquid that is not evaporated in the flash evaporation process is a concentrated aqueous phase, and the vapor collected by condensation is a dilute aqueous phase;
(2) the solid phase precipitated in the flash evaporation process is treated according to the steps (2.1) to (2.7):
(2.1) solid phase melting:
melting the solid phase; step (2.1) is a melt treatment at 950 ℃ for 11 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 100 ℃, and then mixing the molten solid phase with the distilled water phase according to the mass ratio of the solid phase to the distilled water phase of 1:3 preparing a salt solution;
(2.3) insoluble matter conversion
Adding an insoluble substance conversion medicament into the salt solution obtained in the step (2.2), fully treating, namely adding 50g of 200-mesh light calcium carbonate serving as the insoluble substance conversion medicament into each liter of salt solution, stirring for 60 minutes at the temperature of 50 ℃ at the speed of 10rmp, and then carrying out solid-liquid separation;
the insoluble substance conversion agent can be recycled for 30 times after solid-liquid separation.
(2.4) first-order adsorption
And (4) adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular activated carbon with the granularity of 10-24 meshes as the salt solution primary adsorbent, adding 100g of activated carbon into each liter of salt solution, stirring for 60 minutes at the temperature of 40 ℃ at the speed of 10rmp, and then carrying out solid-liquid separation on the salt solution and the used salt solution primary adsorbent.
(2.5) Secondary adsorption
An adsorption bed layer is formed by a salt solution secondary adsorbent, and the salt solution is collected after the liquid separated in the step (2.4) passes through the adsorption bed layer; the macroporous strongly basic styrene anion exchange resin with the model number D201 is used as a secondary adsorbent of a salt solution and is filled into a column to form an adsorption bed layer with the height of 15cm, the dosage of the secondary adsorbent of the salt solution is 1/40 of the volume of the salt solution collected after the step (2.4) is completed, the temperature of the salt solution is kept at 40 ℃, the salt solution passes through the adsorption bed layer at the speed of 1BV/h, and the salt solution which continuously flows out and the resin which completes the secondary adsorption of the salt solution are respectively collected.
(2.6) evaporative crystallization
And (3) evaporating and crystallizing the salt solution collected in the step (2.5), wherein a crystallization solid phase is recovered sodium chloride. The distilled water obtained by evaporation and condensation is reused in step (2.2).
(3) The light water phase separated out in the flash evaporation process needs to be treated according to the steps (3.1) - (3.2):
(3.1) primary adsorption of a fresh water phase:
and (2) adding a fresh water phase primary adsorbent (the activated carbon used in the step (2.4)) into the fresh water phase collected in the step (1), fully treating, namely adding 20g of activated carbon into each liter of fresh water phase, stirring for 60 minutes at the temperature of 40 ℃ at the speed of 10rmp, and then carrying out solid-liquid separation on the fresh water phase and the fresh water phase primary adsorbent.
(3.2) fresh-water phase two-stage adsorption
And (3) forming an adsorption bed layer by using a fresh water phase secondary adsorbent (the adsorbent used in the step (2.5)), and carrying out solid-liquid separation after the fresh water phase treated in the step (3.1) passes through the adsorption bed layer. The used macroporous strongly basic styrene anion exchange resin of D201 is used as a fresh water phase secondary adsorbent, the fresh water phase secondary adsorbent is filled into a column to form an adsorption bed layer with the height of 15cm, the using amount of the fresh water phase secondary adsorbent is 1/40 of the volume of a fresh water phase to be treated, the temperature of the fresh water phase is kept at 40 ℃, the fresh water phase is enabled to pass through the adsorption bed layer at the speed of 1BV/h, and the continuously flowing fresh water phase and the resin for completing the fresh water phase secondary adsorption are respectively collected.
(4) Mixing the non-evaporated concentrated aqueous phase with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater in the flash evaporation process, and then carrying out flash evaporation phase splitting according to the method (1).
And (3) testing results:
for examples 1 to 3, the sodium chloride content, the total TOC content, the total phosphorus content, and the fluorine content were measured for the raw wastewater, the sodium chloride evaporated and crystallized in step (7), and the fresh water phase subjected to the secondary adsorption treatment in step (9), respectively, and the results are shown in table 1:
Claims (10)
1. a method for treating high-salt organic wastewater containing phosphorus and fluorine and recovering salt is characterized by comprising the following steps:
(1) carrying out flash evaporation phase separation on the phosphorus-containing fluorine-containing high-salt organic wastewater to form a concentrated water phase and a light water phase, and after a solid phase is separated out, carrying out treatment according to the steps (2) to (4) which are not in sequence; wherein, the liquid which is not evaporated in the flash evaporation process is a concentrated aqueous phase, and the steam collected by condensation is a fresh aqueous phase;
(2) the solid phase precipitated in the flash evaporation process is treated according to the steps (2.1) to (2.7):
(2.1) solid phase melting:
melting the solid phase;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1), and preparing a salt solution with water;
(2.3) insoluble matter conversion
Adding insoluble substance conversion agent calcium carbonate into the salt solution obtained in the step (2.2), fully treating, and carrying out solid-liquid separation;
(2.4) first-order adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), and carrying out solid-liquid separation after full treatment;
(2.5) Secondary adsorption
An adsorption bed layer is formed by a salt solution secondary adsorbent, and the salt solution is collected after the liquid separated in the step (2.4) passes through the adsorption bed layer;
(2.6) evaporative crystallization
Evaporating and crystallizing the salt solution collected in the step (2.5), wherein a crystallization solid phase is recovered sodium chloride;
(3) the light water phase separated out in the flash evaporation process needs to be treated according to the steps (3.1) - (3.2):
(3.1) primary adsorption of a fresh water phase:
adding a fresh water phase primary adsorbent into the fresh water phase collected in the step (1), fully treating, and performing solid-liquid separation;
(3.2) fresh Water phase two-stage adsorption
And (3) forming an adsorption bed layer by using a fresh water phase secondary adsorbent, and carrying out solid-liquid separation after the fresh water phase treated in the step (3.1) passes through the adsorption bed layer to obtain the treated fresh water phase.
(4) Mixing the non-evaporated concentrated aqueous phase with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater in the flash evaporation process, and then carrying out flash evaporation phase splitting according to the method (1).
2. The method for treating and recycling the high-salinity organic wastewater containing phosphorus and fluorine according to claim 1, which is characterized in that: in the step (1), the flash evaporation phase separation is as follows: the phosphorus-containing and fluorine-containing high-salt organic wastewater forms a concentrated water phase and a fresh water phase through flash evaporation and phase separation and separates out a solid phase.
3. The method for treating the phosphorus-containing fluorine-containing high-salt organic wastewater and recovering the salt according to claim 1 or 2, wherein in the step (1): the water quality of the phosphorus-containing fluorine-containing high-salt organic wastewater is characterized in that the pH value is 6-9, the mass fraction of sodium chloride is 15-30%, the TOC content is 5000-9000 mg/L, the total phosphorus content is 300-650 mg/L, and the fluorine content is 300-500 mg/L.
4. The method for treating the phosphorus-containing fluorine-containing high-salt organic wastewater and recovering the salt according to claim 1, wherein in the step (2):
step (2.1) is to melt and process for 8 to 15 minutes at the temperature of 900 to 1000 ℃;
in the step (2.3), 10g to 50g of insoluble substance conversion medicament is added into each liter of salt solution, and the mixture is stirred for 20 minutes to 60 minutes at the speed of 10rpm (revolutions per minute) to 150rpm within the temperature range of 50 ℃ to 90 ℃.
5. The method for treating the phosphorus-containing fluorine-containing high-salt organic wastewater and recovering the salt according to claim 4, wherein in the step (2):
the insoluble substance conversion medicament in the step (2.3) is light calcium carbonate with 200 meshes to 800 meshes;
the salt solution primary adsorbent in the step (2.4) is granular activated carbon with 10 meshes to 80 meshes;
and (3) the salt solution secondary adsorbent in the step (2.5) is D201 type macroporous strongly basic styrene anion exchange resin.
6. The method for treating and recycling the high-salinity organic wastewater containing phosphorus and fluorine according to claim 4, characterized in that:
the distilled water used for dissolving in the step (2.2) is distilled water condensed and recovered in the evaporation crystallization process of the step (2.6) and externally supplemented distilled water; the sodium chloride collected by the evaporation and crystallization in the step (2.6) can be used for industrial application, and the distilled water obtained by evaporation and condensation can be reused in the step (2.2).
7. The method for treating and recycling the high-salinity organic wastewater containing phosphorus and fluorine according to claim 4, characterized in that: and (3) recycling the insoluble substance conversion medicament in the step (2.3) for 20-30 times after solid-liquid separation.
8. The method for treating the phosphorus-containing fluorine-containing high-salt organic wastewater and recovering the salt according to claim 1, wherein in the step (3):
in the step (3.1), 20g to 100g of the fresh water phase primary adsorbent is added into each liter of the fresh water phase, the mixture is stirred for 20 minutes to 60 minutes at the temperature of 40 ℃ to 70 ℃ at the speed of 10rpm to 150rpm, and the fresh water phase primary adsorbent are separated and collected;
in the step (3.2), an adsorption bed layer with the height of 15-45 cm is formed by the fresh water phase secondary adsorbent, the temperature of the fresh water phase is kept at 40-70 ℃, the fresh water phase is made to pass through the adsorption bed layer at the speed of 1BV/h (bed volume/hour) to 5BV/h, the fresh water phase secondary adsorbent in unit volume needs to process 20-40 times volume of the fresh water phase, the impurity removal is completed through the fresh water phase of the adsorption bed layer, the fresh water phase secondary adsorbent can be discharged or used for other purposes, and the fresh water phase secondary adsorbent is collected.
9. The method for treating and recycling the high-salinity organic wastewater containing phosphorus and fluorine according to claim 8, characterized in that:
the fresh water phase primary adsorbent in the step (3.1) is granular activated carbon;
the fresh water phase secondary adsorbent in the step (3.2) is D201 type macroporous strongly basic styrene anion exchange resin.
10. The method for treating and recycling the phosphorus-containing fluorine-containing high-salt organic wastewater according to claim 9, characterized in that:
the fresh water phase primary adsorbent in the step (3.1) is a salt solution primary adsorbent which is not treated after the step (2.4) is completed; after the step (3.1) is completed, the fresh water phase first-stage adsorbent can be regenerated and recycled by adopting methods such as thermal regeneration and the like;
the fresh water phase secondary adsorbent in the step (3.2) is a salt solution secondary adsorbent which is not treated after the step (2.5) is completed; after the step (3.2) is completed, the fresh water phase secondary adsorbent can be regenerated and recycled by adopting methods of firstly alkali washing and then water washing and the like.
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