CN114605018B - Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt - Google Patents
Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt Download PDFInfo
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- CN114605018B CN114605018B CN202210115130.4A CN202210115130A CN114605018B CN 114605018 B CN114605018 B CN 114605018B CN 202210115130 A CN202210115130 A CN 202210115130A CN 114605018 B CN114605018 B CN 114605018B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 56
- 239000011574 phosphorus Substances 0.000 title claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 52
- 239000011737 fluorine Substances 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 50
- 150000003839 salts Chemical class 0.000 title description 17
- 239000013505 freshwater Substances 0.000 claims abstract description 122
- 238000001179 sorption measurement Methods 0.000 claims abstract description 75
- 238000001704 evaporation Methods 0.000 claims abstract description 65
- 230000008020 evaporation Effects 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000011780 sodium chloride Substances 0.000 claims abstract description 22
- 238000005191 phase separation Methods 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims description 138
- 239000012266 salt solution Substances 0.000 claims description 90
- 239000003463 adsorbent Substances 0.000 claims description 88
- 239000007790 solid phase Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 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 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003957 anion exchange resin Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000012043 crude product 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
- 238000004519 manufacturing process Methods 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 239000002253 acid Substances 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
- 229920001429 chelating resin Polymers 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000008394 flocculating agent Substances 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a method for treating and recovering high-salt organic wastewater containing phosphorus and fluorine. Firstly separating the wastewater into a concentrated water phase and a fresh water phase through flash evaporation phase separation, separating out solids, and then treating the concentrated water phase, the fresh water phase and the separated-out solids to obtain an industrially recyclable sodium chloride product on the basis of removing impurity phosphorus and impurity fluorine and reducing TOC content; the flash evaporation phase separation, melting, dissolution, insoluble matter conversion, adsorption and other steps adopted by the method have the characteristics of simple operation, simple equipment, easy maintenance and convenient popularization and application, and have the advantages of 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 the 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 especially 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 the environment pollution is caused; in addition, because phosphorus, fluorine and TOC are difficult to thoroughly remove, the quality of sodium chloride recovered from the wastewater is low, and the sodium chloride cannot be effectively utilized, so that resource waste is caused.
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 is required to be washed by a special washing liquid to remove phosphorus in the inorganic salt crude product, and the washed inorganic salt crude product is contacted with oxygen-containing gas at high temperature and 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-concentration water is further subjected to more complicated treatment, namely, the medium-concentration water is introduced into a graphene adsorption tower to be adsorbed and filtered, so that organic matters such as greasy dirt and the like are removed; introducing the deoiled medium-concentration water into an evaporator to obtain crystalline solid powder and mixed gas; introducing the mixed gas into a gas membrane separator for separation to obtain pure water and enriched mixed gas; introducing the thickened mixed gas into a condenser for condensation treatment to obtain water and non-condensable gas; introducing non-condensable gas into a microwave ultraviolet catalytic reactor for decomposition to obtain CO and HO.
In the prior art, the technology is also a series of complex process treatments such as dissolution, multi-connection reaction, tubular membrane system treatment, water quality adjustment (acid adjustment), activated carbon adsorption, fluoride ion adsorption, ammonia nitrogen adsorption, nanofiltration treatment, chelating resin adsorption, evaporation crystallization and the like.
In the prior art, high-salt wastewater is separated into a fresh water phase and a salt-containing solid phase by adopting evaporation crystallization, but when organic matters are contained in the wastewater, the fresh water phase contains impurities due to factors such as entrainment, and the fresh water quality needs to be further improved by a biological method and the like, for example, condensate formed after evaporation in the high-salt organic wastewater is provided with a biological treatment area for removing the organic matters; and a large amount of organic impurities remain in the salt-containing solid phase, so that the solid phase is still dangerous waste. Although the salt-containing solid phase can reduce the Total Organic Carbon (TOC) content in the salt-containing solid phase by incineration and other methods, in view of the fact that phosphorus and fluorine impurities are introduced in the production process of pesticides, phosphate fertilizers and the like, the impurities remain in the solid phase after incineration, so that the quality of the recovered sodium chloride is poor and cannot be industrially recycled. For such impurity-containing waste salts, the salt solution can be subjected to precipitation impurity removal by adding a precipitant, a flocculating agent and the like, for example, impurity phosphorus is partially removed by adding calcium chloride into the glyphosate production wastewater; adding complexing agents consisting of polyaluminium sulfate, polyferric sulfate, zirconia, active titanium dioxide, water and a fixative into the wastewater of coal chemical industry to remove fluorine; the method comprises the following steps of adding a compound flocculant consisting of hydrogen peroxide, polyaluminium chloride, inorganic aluminum salt and inorganic cerium salt into electroplating wastewater, and removing impurity phosphorus and fluorine in the wastewater. However, the precipitation or flocculation has limited impurity removal effect and new impurities are introduced due to the addition of the precipitant or flocculant, making it difficult to ensure the quality of the recovered salt. Although the membrane separation method can remove impurities in high-salt water without introducing secondary pollution, for example, a nanofiltration membrane is used for intercepting inorganic phosphorus and organic phosphorus in salt-containing wastewater, the method has the problems of high equipment cost, membrane pollution and the like.
Therefore, at present, no integrated treatment mode for the phosphorus-containing fluorine-containing high-salt organic wastewater exists, and the existing technologies such as a biological method, an incineration method, a chemical precipitation method, a membrane separation method and the like can partially realize the purposes 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, secondary pollution introduction, excessive 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 of:
(1) Forming a concentrated water phase and a fresh water phase from the phosphorus-containing fluorine-containing high-salt organic wastewater through flash evaporation phase separation, separating out a solid phase, and treating according to the steps (2) to (4) in no-sequence; wherein the liquid which is not evaporated in the flash evaporation process is a concentrated water phase, and the vapor collected by condensation is a fresh water phase;
(2) The solid phase precipitated in the flash evaporation process is treated according to steps (2.1) to (2.7):
(2.1) solid phase melting:
melt-treating 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) Primary adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), and performing solid-liquid separation after full treatment;
(2.5) two-stage adsorption
Forming an adsorption bed layer by a salt solution secondary adsorbent, and collecting the salt solution 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 the solid phase of crystallization is recovered sodium chloride.
(3) The fresh water phase separated out in the flash evaporation process is treated according to steps (3.1) to (3.2):
(3.1) first-stage adsorption of fresh water phase:
adding a fresh water phase primary adsorbent into the fresh water phase collected in the step (1), fully treating, and then carrying out solid-liquid separation;
(3.2) fresh water phase two-stage adsorption
And (3) forming an adsorption bed layer by the fresh water phase secondary adsorbent, and carrying out solid-liquid separation on the fresh water phase treated in the step (3.1) after passing through the adsorption bed layer to obtain a treated fresh water phase.
(4) And (3) mixing the non-evaporated concentrated water phase in the flash evaporation process with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater, and performing flash evaporation phase separation in the mode of (1).
Further, in step (1), flash separation is: the organic wastewater containing phosphorus and fluorine and high salt is preheated to 95-105 ℃, the flash evaporation pressure is set to 55-70 Kpa, and a concentrated water phase and a fresh water phase are formed through flash evaporation phase separation, and a solid phase is separated out.
Further, in step (1): the phosphorus-containing fluorine-containing high-salt organic wastewater is characterized in that the pH 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 step (2): preferably, the step (2.1) is to perform the melting treatment for 8 to 15 minutes at the temperature ranging from 900 to 1000 ℃; preferably, in the step (2.2), the molten solid phase treated in the step (2.1) is firstly cooled to a temperature ranging from 100 ℃ to 200 ℃, and then is prepared into a salt solution according to the mass ratio of the cooled solid phase to distilled water of 1:3 to 1:5; preferably, in the step (2.3), 10g to 50g of the insoluble matter-converting agent is added to each liter of the salt solution, and stirred at a rate of 10rpm (revolutions per minute) to 150rpm for 20 minutes to 60 minutes at a temperature ranging from 50 ℃ to 90 ℃; preferably, in the step (2.4), 20g to 100g of the primary adsorbent of the salt solution is added to the liquid separated in the step (2.3), and the mixture is stirred at a speed of 10rpm to 150rpm for 20 minutes to 60 minutes at a temperature ranging from 40 ℃ to 70 ℃; preferably, in the step (2.5), an adsorption bed layer with the height of 15 cm-45 cm is formed by a salt solution secondary adsorbent, the salt solution is kept at the temperature of 40-70 ℃ and is enabled to pass through the adsorption bed layer at the speed of 1BV/h (bed volume/h) to 5BV/h, the salt solution of 20-40 times of volume is required to be treated by the unit volume of the salt solution secondary adsorbent, and the salt solution passing through the adsorption bed layer and the salt solution secondary adsorbent with the secondary adsorption are respectively collected; preferably, in the step (2.6), evaporating and crystallizing the salt solution, wherein the solid phase of the crystallization is recovered sodium chloride, and distilled water obtained by evaporating and condensing is recycled in the step (2.2);
further, in step (2): preferably, the insoluble substance conversion agent in the step (2.3) is light calcium carbonate with 200-800 meshes; preferably, the salt solution primary adsorbent in the step (2.4) is granular activated carbon with 10-80 meshes; preferably, the salt solution secondary adsorbent in the step (2.5) is D201 type macroporous strong basic styrene anion exchange resin;
further, the distilled water used for dissolution in the step (2.2) is from distilled water recovered by condensation in the evaporation and crystallization process of the step (2.6) and external supplementary distilled water; the sodium chloride collected by the evaporation and crystallization in the step (2.6) can be used for industrial application, and distilled water obtained by evaporation and condensation can be recycled in the step (2.2).
Further, the insoluble substance conversion agent in the step (2.3) needs to be recycled for 20-30 times after solid-liquid separation.
Further, in step (3): preferably, in the step (3.1), 20g to 100g of the fresh water phase primary adsorbent is added into each liter of fresh water phase, stirring is carried out for 20 minutes to 60 minutes at a speed of 10rpm to 150rpm at a temperature of 40 ℃ to 70 ℃, solid-liquid separation is carried out, and the fresh water phase primary adsorbent are collected; preferably, in the step (3.2), an adsorption bed layer with the height of 15 cm-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 passes through the adsorption bed layer according to the speed of 1BV/h (volume/h of the bed layer) to 5BV/h, the fresh water phase secondary adsorbent in unit volume needs to treat 20-40 times of volume of the fresh water phase, impurities are removed through the fresh water phase of the adsorption bed layer, and the fresh water phase secondary adsorbent can be discharged or used otherwise and 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 strong-alkaline styrene anion exchange resin.
Further, the fresh water phase primary adsorbent in the step (3.1) is an untreated salt solution primary adsorbent after the step (2.4) is completed; after the step (3.1) is completed, the fresh water phase primary 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 alkali washing, water washing and the like.
After the technical scheme is adopted, the invention mainly has the following effects:
1. by adopting the method, the high-removal-rate phosphorus and fluorine removal can be realized simultaneously on the premise of not introducing new impurities, and the contents of impurity phosphorus, impurity fluorine and TOC in the salt solution can be further reduced.
2. The operation is simple, the equipment is simple, the maintenance is easy, and the popularization and the application are convenient. The flash evaporation phase separation, solid phase melting, dissolution, insoluble matter conversion, primary adsorption, secondary adsorption and evaporative crystallization steps of the salt solution and fresh water phases are low in requirements on operation and equipment, and the method is easy to maintain and popularize.
3. Low cost and good economical efficiency. The insoluble matter converting medicine and adsorbent adopted in the method of the invention are easy to obtain, have low price, can be recycled, cascade utilized and regenerated for multiple times, and compared with the prior art, the method can save material consumption and reduce the cost of wastewater treatment and salt recovery.
4. Fully recycling resources and being beneficial to environmental protection. Firstly, separating the phosphorus-containing fluorine-containing high-salt organic wastewater into a concentrated water phase and a fresh water phase by a flash evaporation phase separation mode, and separating out a solid phase; mixing the concentrated water phase which is still the organic wastewater containing phosphorus and fluorine and high salt with the wastewater of the next batch, and then carrying out flash evaporation phase separation again to ensure that the wastewater is not discharged; after the fresh water phase obtained by flash evaporation phase separation is subjected to two steps of first-stage adsorption and second-stage adsorption of the fresh water phase, the TOC content in the fresh water phase is effectively reduced, and the aim of being beneficial to environmental protection is fulfilled; the solid phase separated by flash evaporation phase separation is recovered to high-quality sodium chloride after the steps of solid phase melting, dissolution, insoluble matter conversion, primary adsorption of salt solution, secondary adsorption of salt solution, evaporation crystallization and the like are sequentially carried out, so that the aim of fully recovering resources is fulfilled.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
Detailed Description
The present invention is further described below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples. Various substitutions and alterations are made according to the ordinary skill and familiar means of the art without departing from the technical spirit of the invention, and all such substitutions and alterations are intended to be included in the scope of the invention.
Example 1:
a method for treating and recovering high-salt organic wastewater containing phosphorus and fluorine is characterized in that:
(1) The embodiment adopts the phosphorus-containing fluorine-containing high-salt organic wastewater as an experimental object, and has the water quality characteristics of pH of 6.2, sodium chloride mass fraction of 21.64%, TOC content average value of 8455mg/L, total phosphorus content of 628.2mg/L and fluorine content of 330.4mg/L.
The organic wastewater containing phosphorus and fluorine and high salt is preheated to 100 ℃, the flash evaporation pressure is set to 60Kpa, and a concentrated water phase and a fresh water phase are formed through flash evaporation phase separation, and a solid phase is separated out.
Processing according to the steps (2) to (4) which are not sequenced; it is worth noting that the liquid not evaporated during the flash evaporation is a concentrated aqueous phase, and the vapor collected by condensation is a fresh aqueous phase;
(2) The solid phase precipitated in the flash evaporation process is treated according to steps (2.1) to (2.7):
(2.1) solid phase melting:
melt-treating the solid phase; step (2.1) is a melting treatment at 1000 ℃ for 8 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 150 ℃ firstly, and then carrying out distillation according to the mass ratio of the solid phase to the distilled water phase of 1:4, preparing a salt solution in proportion;
(2.3) insoluble matter conversion
Adding an insoluble matter conversion reagent into the salt solution in the step (2.2), fully treating, namely adding 30g of light calcium carbonate with 600 meshes into each liter of salt solution as the insoluble matter conversion reagent, stirring at the temperature of 70 ℃ for 40 minutes at the rate of 80rmp, and then carrying out solid-liquid separation;
the insoluble matter conversion medicament can be recycled for 25 times after solid-liquid separation.
(2.4) Primary adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular active carbon with the granularity of 46-60 meshes as the salt solution primary adsorbent, adding 60g of active carbon into each liter of salt solution, stirring at the temperature of 55 ℃ for 40 minutes at the rate of 80rmp, and then separating the salt solution from the used salt solution primary adsorbent.
(2.5) two-stage adsorption
Forming an adsorption bed layer by a salt solution secondary adsorbent, and collecting the salt solution after the liquid separated in the step (2.4) passes through the adsorption bed layer; the macroporous strong-alkaline styrene anion exchange resin with the model D201 is used as a salt solution secondary adsorbent and is filled into an adsorption bed layer with the column height of 30cm, the dosage of the salt solution secondary adsorbent 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 is made to pass through the adsorption bed layer at the speed of 3BV/h, and continuously flowing salt solution and resin for completing the salt solution secondary adsorption are respectively collected.
(2.6) evaporative crystallization
Evaporating and crystallizing the salt solution collected in the step (2.5), wherein the solid phase of crystallization is recovered sodium chloride. In the step (2.6), evaporating and crystallizing the salt solution, wherein the solid phase of the crystallization is recovered sodium chloride, and distilled water obtained by evaporating and condensing is recycled in the step (2.2).
(3) The fresh water phase separated out in the flash evaporation process is treated according to steps (3.1) to (3.2):
(3.1) first-stage adsorption of fresh water phase:
adding a fresh water phase primary adsorbent (activated carbon after use in step 2.4) into the fresh water phase collected in step (1), fully treating, namely adding 60g of activated carbon into each liter of fresh water phase, stirring at a speed of 80rmp for 40 minutes at a temperature of 55 ℃, 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 a fresh water phase secondary adsorbent (adsorbent after the use 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 macroporous strong alkaline styrene anion exchange resin of D201 is used as a fresh water phase secondary adsorbent, the fresh water phase secondary adsorbent is filled into an adsorbent bed with column height of 30cm, the dosage of the fresh water phase secondary adsorbent is 1/25 of the volume of the 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 adsorbent bed at a speed of 3BV/h, and the fresh water phase which continuously flows out and the resin which completes the secondary adsorption of the fresh water phase are respectively collected.
(4) And (3) mixing the non-evaporated concentrated water phase in the flash evaporation process with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater, and performing flash evaporation phase separation in the mode of (1).
Example 2:
a method for treating and recovering high-salt organic wastewater containing phosphorus and fluorine is characterized in that:
(1) The embodiment adopts the phosphorus-containing fluorine-containing high-salt organic wastewater as an experimental object, and has the water quality characteristics of pH 7.3, sodium chloride mass fraction 28.52%, TOC content average value 6246.5mg/L, total phosphorus content 434.1mg/L and fluorine content 378mg/L.
The organic wastewater containing phosphorus and fluorine and high salt is preheated to 95 ℃, the flash evaporation pressure is set to 55Kpa, and a concentrated water phase and a fresh water phase are formed through flash evaporation phase separation, and a solid phase is separated out.
Processing according to the steps (2) to (4) which are not sequenced; it is worth noting that the liquid not evaporated during the flash evaporation is a concentrated aqueous phase, and the vapor collected by condensation is a fresh aqueous phase;
(2) The solid phase precipitated in the flash evaporation process is treated according to steps (2.1) to (2.7):
(2.1) solid phase melting:
melt-treating the solid phase; step (2.1) is a melting treatment at 900 ℃ for 15 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 200 ℃, and then carrying out distillation according to the mass ratio of the solid phase to the distilled water phase of 1:5, preparing a salt solution in proportion;
(2.3) insoluble matter conversion
Adding an insoluble matter conversion reagent into the salt solution in the step (2.2), fully treating, namely adding 10g of light calcium carbonate with the granularity of 800 meshes into each liter of salt solution as the insoluble matter conversion reagent, stirring at the temperature of 90 ℃ for 20 minutes at the speed of 150rmp, and then carrying out solid-liquid separation;
the insoluble matter conversion medicament can be recycled for 20 times after solid-liquid separation.
(2.4) Primary adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular active carbon with granularity of 60-80 meshes as the salt solution primary adsorbent, adding 20g of active carbon into each liter of salt solution, stirring at the temperature of 70 ℃ for 20 minutes at the speed of 150rmp, and then separating the salt solution from the used salt solution primary adsorbent.
(2.5) two-stage adsorption
Forming an adsorption bed layer by a salt solution secondary adsorbent, and collecting the salt solution after the liquid separated in the step (2.4) passes through the adsorption bed layer; the macroporous strong-alkaline styrene anion exchange resin with the model D201 is used as a salt solution secondary adsorbent and is filled into an adsorption bed layer with the column height of 45cm, the dosage of the salt solution secondary adsorbent 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 is made to pass through the adsorption bed layer at the speed of 5BV/h, and continuously flowing salt solution and resin for completing the salt solution secondary adsorption are respectively collected.
(2.6) evaporative crystallization
Evaporating and crystallizing the salt solution collected in the step (2.5), wherein the solid phase of crystallization is recovered sodium chloride. The distilled water obtained by evaporation and condensation is recycled in the step (2.2).
(3) The fresh water phase separated out in the flash evaporation process is treated according to steps (3.1) to (3.2):
(3.1) first-stage adsorption of fresh water phase:
adding a fresh water phase primary adsorbent (activated carbon after use in step 2.4) into the fresh water phase collected in step (1), fully treating, namely adding 20g of activated carbon into each liter of fresh water phase, stirring at a rate of 150rmp for 20 minutes at a temperature of 70 ℃, 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 a fresh water phase secondary adsorbent (adsorbent after the use 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 macroporous strong alkaline styrene anion exchange resin of D201 is used as a fresh water phase secondary adsorbent, the fresh water phase secondary adsorbent is filled into an adsorbent bed with a column 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 adsorbent bed at a speed of 5BV/h, and the fresh water phase which continuously flows out and the resin which completes the secondary adsorption of the fresh water phase are respectively collected.
(4) And (3) mixing the non-evaporated concentrated water phase in the flash evaporation process with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater, and performing flash evaporation phase separation in the mode of (1).
Example 3:
a method for treating and recovering high-salt organic wastewater containing phosphorus and fluorine is characterized in that:
(1) The embodiment adopts the phosphorus-containing fluorine-containing high-salt organic wastewater as an experimental object, and is characterized in that the water quality is pH 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 476.7mg/L.
The organic wastewater containing phosphorus and fluorine and high salt is preheated to 105 ℃, the flash evaporation pressure is set to be 70Kpa, and a concentrated water phase and a fresh water phase are formed through flash evaporation phase separation, and a solid phase is separated out.
Processing according to the steps (2) to (4) which are not sequenced; it is worth noting that the liquid not evaporated during the flash evaporation is a concentrated aqueous phase, and the vapor collected by condensation is a fresh aqueous phase;
(2) The solid phase precipitated in the flash evaporation process is treated according to steps (2.1) to (2.7):
(2.1) solid phase melting:
melt-treating the solid phase; step (2.1) is a melting treatment at 950 ℃ for 11 minutes;
(2.2) dissolution:
cooling the molten solid phase treated in the step (2.1) to 100 ℃, and then carrying out mass ratio of the solid phase to distilled water phase to be 1:3, preparing a salt solution in proportion;
(2.3) insoluble matter conversion
Adding an insoluble matter conversion reagent into the salt solution in the step (2.2), fully treating, namely adding 50g of 200-mesh light calcium carbonate serving as the insoluble matter conversion reagent into each liter of salt solution, stirring at the temperature of 50 ℃ for 60 minutes at the speed of 10rmp, and then carrying out solid-liquid separation;
the insoluble matter conversion medicament can be recycled for 30 times after solid-liquid separation.
(2.4) Primary adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), fully treating, namely using granular active carbon with the granularity of 10-24 meshes as the salt solution primary adsorbent, adding 100g of active carbon into each liter of salt solution, stirring at the temperature of 40 ℃ for 60 minutes at the speed of 10rmp, and then separating the salt solution from the used salt solution primary adsorbent.
(2.5) two-stage adsorption
Forming an adsorption bed layer by a salt solution secondary adsorbent, and collecting the salt solution after the liquid separated in the step (2.4) passes through the adsorption bed layer; namely, the macroporous strong-alkali styrene anion exchange resin with the model D201 is used as a salt solution secondary adsorbent and is filled into an adsorption bed layer with the column height of 15cm, the dosage of the salt solution secondary adsorbent 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 is made to pass through the adsorption bed layer at the speed of 1BV/h, and continuously flowing salt solution and resin for completing the salt solution secondary adsorption are respectively collected.
(2.6) evaporative crystallization
Evaporating and crystallizing the salt solution collected in the step (2.5), wherein the solid phase of crystallization is recovered sodium chloride. The distilled water obtained by evaporation and condensation is recycled in the step (2.2).
(3) The fresh water phase separated out in the flash evaporation process is treated according to steps (3.1) to (3.2):
(3.1) first-stage adsorption of fresh water phase:
adding a fresh water phase primary adsorbent (activated carbon after use in step 2.4) into the fresh water phase collected in step (1), fully treating, namely adding 20g of activated carbon into each liter of fresh water phase, stirring at a rate of 10rmp for 60 minutes at a temperature of 40 ℃, 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 a fresh water phase secondary adsorbent (adsorbent after the use 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 macroporous strong alkaline styrene anion exchange resin of D201 is used as a fresh water phase secondary adsorbent, the fresh water phase secondary adsorbent is filled into an adsorbent bed with column height of 15cm, the dosage of the fresh water phase secondary adsorbent is 1/40 of the volume of the 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 adsorbent bed at a speed of 1BV/h, and the fresh water phase which continuously flows out and the resin which completes the secondary adsorption of the fresh water phase are respectively collected.
(4) And (3) mixing the non-evaporated concentrated water phase in the flash evaporation process with the next batch of phosphorus-containing fluorine-containing high-salt organic wastewater, and performing flash evaporation phase separation in the mode of (1).
Test results:
for examples 1 to 3, the sodium chloride content, total TOC content, total phosphorus content, and fluorine content were measured for the raw wastewater, the evaporated and crystallized sodium chloride in step (7), and the fresh water phase after the second adsorption treatment in step (9), respectively, and the results are shown in table 1:
Claims (7)
1. a method for treating and recovering high-salt organic wastewater containing phosphorus and fluorine is characterized in that:
(1) Forming a concentrated water phase and a fresh water phase from the phosphorus-containing fluorine-containing high-salt organic wastewater through flash evaporation phase separation, separating out a solid phase, and treating according to the steps (2) to (4) in no-sequence; wherein the liquid which is not evaporated in the flash evaporation process is a concentrated water phase, and the vapor collected by condensation is a fresh water phase;
(2) The solid phase precipitated in the flash evaporation process is treated according to steps (2.1) to (2.7):
(2.1) solid phase melting:
melt-treating 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) Primary adsorption
Adding a salt solution primary adsorbent into the liquid separated in the step (2.3), and performing solid-liquid separation after full treatment;
(2.5) two-stage adsorption
Forming an adsorption bed layer by a salt solution secondary adsorbent, and collecting the salt solution 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 the solid phase of crystallization is recovered sodium chloride;
(3) The fresh water phase separated out in the flash evaporation process is treated according to steps (3.1) to (3.2):
(3.1) first-stage adsorption of fresh water phase:
adding a fresh water phase primary adsorbent into the fresh water phase collected in the step (1), fully treating, and then carrying out solid-liquid separation;
(3.2) fresh water phase two-stage adsorption
Forming an adsorption bed layer by a fresh water phase secondary adsorbent, and carrying out solid-liquid separation on the fresh water phase treated in the step (3.1) after passing through the adsorption bed layer to obtain a treated fresh water phase;
(4) Mixing the non-evaporated concentrated water 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 separation in the mode of the step (1);
in the step (1), flash evaporation phase separation is as follows: forming a concentrated water phase and a fresh water phase from the phosphorus-containing fluorine-containing high-salt organic wastewater through flash evaporation phase separation, and separating out a solid phase;
in the step (2):
the insoluble substance conversion medicament in the step (2.3) is light calcium carbonate with the mesh size of 200-800;
the primary adsorbent of the salt solution in the step (2.4) is granular active carbon with 10-80 meshes;
the salt solution secondary adsorbent in the step (2.5) is D201 type macroporous strong-alkaline styrene anion exchange resin;
in the step (3):
in the step (3.1), 20 g-100 g of the fresh water phase primary adsorbent is added into each liter of fresh water phase, stirring is carried out for 20 minutes-60 minutes at the speed of 10 rpm-150 rpm at the temperature of 40-70 ℃, solid-liquid separation is carried out, and the fresh water phase primary adsorbent are collected;
in the step (3.2), an adsorption bed layer with the height of 15 cm-45 cm is formed by a fresh water phase secondary adsorbent, the temperature of the fresh water phase is kept at 40-70 ℃, the fresh water phase is enabled to pass through the adsorption bed layer according to the speed of 1 BV/h-5 BV/h, the fresh water phase of 20-40 times of volume is required to be treated by the fresh water phase secondary adsorbent in unit volume, impurity removal is completed through the fresh water phase of the adsorption bed layer, and the fresh water phase secondary adsorbent is discharged or otherwise used and collected.
2. The method for treating and recovering organic wastewater containing phosphorus and fluorine according to claim 1, wherein in the step (1): the phosphorus-containing fluorine-containing high-salt organic wastewater is characterized in that the pH 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.
3. The method for treating and recovering organic wastewater containing phosphorus and fluorine according to claim 1, wherein in the step (2):
step (2.1) is to melt at 900-1000 ℃ for 8-15 minutes;
in the step (2.3), 10g to 50g of the insoluble matter-converting agent is added to each liter of the salt solution, and the mixture is stirred at a rate of 10rpm to 150rpm for 20 minutes to 60 minutes at a temperature ranging from 50 ℃ to 90 ℃.
4. The method for treating and recovering the phosphorus-containing fluorine-containing high-salt organic wastewater, according to claim 3, which is characterized in that: the distilled water used for dissolution in the step (2.2) is from distilled water recovered by condensation in the evaporation and crystallization process of the step (2.6) and external supplementary distilled water; the sodium chloride collected by the evaporation and crystallization in the step (2.6) is used for industrial application, and distilled water obtained by evaporation and condensation is recycled in the step (2.2).
5. The method for treating and recovering the phosphorus-containing fluorine-containing high-salt organic wastewater, according to claim 3, which is characterized in that: and (3) recycling the insoluble substance conversion medicament in the step (2.3) for 20-30 times after solid-liquid separation.
6. The method for treating and recovering the phosphorus-containing fluorine-containing high-salt organic wastewater, which is 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 strong-alkaline styrene anion exchange resin.
7. The method for treating and recovering the phosphorus-containing fluorine-containing high-salt organic wastewater, which is characterized in that: the fresh water phase primary adsorbent in the step (3.1) is an untreated saline solution primary adsorbent after the step (2.4) is completed; after the step (3.1) is completed, the fresh water phase primary adsorbent is regenerated and recycled;
the fresh water phase secondary adsorbent in the step (3.2) is an untreated salt solution secondary adsorbent after the step (2.5) is completed; after the step (3.2) is completed, the fresh water phase secondary adsorbent is regenerated and recycled by adopting a method of alkali washing and then water washing.
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