CN112441601A - System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater - Google Patents
System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater Download PDFInfo
- Publication number
- CN112441601A CN112441601A CN202010781119.2A CN202010781119A CN112441601A CN 112441601 A CN112441601 A CN 112441601A CN 202010781119 A CN202010781119 A CN 202010781119A CN 112441601 A CN112441601 A CN 112441601A
- Authority
- CN
- China
- Prior art keywords
- crystallization
- magnesium sulfate
- sodium chloride
- sludge
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 285
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 256
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 144
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 140
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 128
- 239000002351 wastewater Substances 0.000 title claims abstract description 78
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 75
- 230000023556 desulfurization Effects 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002425 crystallisation Methods 0.000 claims abstract description 184
- 230000008025 crystallization Effects 0.000 claims abstract description 184
- 239000010802 sludge Substances 0.000 claims abstract description 173
- 238000001914 filtration Methods 0.000 claims abstract description 100
- 150000003839 salts Chemical class 0.000 claims abstract description 99
- 238000001728 nano-filtration Methods 0.000 claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims abstract description 83
- 238000000926 separation method Methods 0.000 claims abstract description 74
- 239000003814 drug Substances 0.000 claims abstract description 47
- 239000002244 precipitate Substances 0.000 claims abstract description 45
- 208000005156 Dehydration Diseases 0.000 claims abstract description 40
- 230000018044 dehydration Effects 0.000 claims abstract description 40
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 40
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000006228 supernatant Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 229
- 239000007788 liquid Substances 0.000 claims description 73
- 239000012528 membrane Substances 0.000 claims description 56
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 54
- 230000001105 regulatory effect Effects 0.000 claims description 44
- 229910001424 calcium ion Inorganic materials 0.000 claims description 42
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 37
- 150000002500 ions Chemical class 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011575 calcium Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 23
- 239000012452 mother liquor Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 14
- 239000000347 magnesium hydroxide Substances 0.000 claims description 14
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- -1 and meanwhile Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 8
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 50
- 238000001704 evaporation Methods 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 18
- 239000002562 thickening agent Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical class O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/18—Treatment of sludge; Devices therefor by thermal conditioning
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a system and a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, which comprises a pretreatment device, and a sodium chloride crystallization system and a magnesium sulfate crystallization system which are respectively connected with the pretreatment device, wherein the desulfurization wastewater is softened by the pretreatment device to generate calcium magnesium ion precipitate and supernatant, the supernatant is treated by a filtering device, a nano-filtration salt separation device, a concentration device and a crystallization device in the sodium chloride crystallization system to obtain sodium chloride crystals, and the calcium magnesium ion precipitate is treated by a sludge dehydration device, a heating device, a secondary dehydration device, a second concentration device and a second crystallization device to obtain the magnesium sulfate crystals. The invention provides a process technology aiming at the salinity characteristic of the desulfurization wastewater, can simultaneously recover two types of salinity of magnesium sulfate and sodium chloride in the desulfurization wastewater, not only increases the resource recycling, but also reduces the sludge amount for disposal, is an environment-friendly technology, and adopts common low-price medicaments as medicaments, so that the operation cost is low.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a system and a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater.
Background
At present, zero discharge of desulfurization wastewater of a coal-fired power plant is a hotspot for water environment protection in China, the desulfurization wastewater is used as terminal wastewater of the coal-fired power plant, has the characteristics of high turbidity, high hardness, high salt content, multiple types of pollutants, large water quality fluctuation of different power plants and the like, and is industrial wastewater with great treatment difficulty, the traditional desulfurization wastewater treatment process can only remove suspended substances and heavy metal ions in the wastewater to reach the desulfurization wastewater discharge standard, and the wastewater also contains a large amount of salt to cause serious salt pollution to the water environment, so that the exploration and development of an effective and economic desulfurization wastewater zero discharge process becomes the key point of research of professionals in the technical field.
The existing desulfurization wastewater zero-discharge process can be mainly divided into three types of pretreatment softening, nanofiltration salt separation, membrane concentration and decrement, evaporative crystallization, pretreatment softening, membrane concentration and decrement, flue evaporation, low-temperature flash evaporation and high-temperature flue gas evaporation and the like. The process comprises the steps of pretreatment softening, nanofiltration salt separation, membrane concentration and reduction and evaporative crystallization, wherein lime, sodium hydroxide, soda ash and the like are adopted to carry out softening and clarification treatment on desulfurization wastewater to remove hardness and heavy metal ions in water, then a nanofiltration membrane is adopted to carry out salt separation treatment, a sodium chloride solution generated on a water production side of the nanofiltration membrane is concentrated through a high-pressure membrane, evaporative crystallization is carried out, and sodium chloride crystal salt is finally recovered.
The prior art has certain defects, wherein the processes of pretreatment softening, nanofiltration salt separation, membrane concentration and decrement and evaporative crystallization can only recover sodium chloride crystal salt, is suitable for being applied to desulfurization wastewater with sodium chloride as a main component, has limited application range, and simultaneously, sludge with high-concentration ionic components is directly transported and treated outside, thereby causing secondary pollution to the environment. In the processes of pretreatment softening, membrane concentration and reduction and flue evaporation, no crystal salt is generated, and no salt resource is recovered. In the process of low-temperature flash evaporation and high-temperature flue gas evaporation, pollutants in the desulfurization wastewater are finally evaporated by the high-temperature flue gas and mixed into flue fly ash, which belongs to pollution transfer, influences the utilization of the fly ash of a power plant and increases the power generation coal consumption of the power plant. In addition, the air and smoke system is an open cycle, although most of salt is attached to dust and trapped, the salt which is not trapped can be discharged into the atmosphere along with the smoke, and the risk of haze aggravation by the salt is potential;
disclosure of Invention
The invention provides a process technology aiming at the salinity characteristic of the desulfurization wastewater, can simultaneously recover two types of salinity of magnesium sulfate and sodium chloride in the desulfurization wastewater, not only increases the resource recycling, but also reduces the sludge amount for disposal, is an environment-friendly technology, and adopts common low-price medicaments as medicaments, so that the operation cost is low.
The invention provides a system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, which comprises a pretreatment device, and a sodium chloride crystallization system and a magnesium sulfate crystallization system which are respectively connected with the pretreatment device;
the pretreatment device comprises a pretreatment device tank body, a pretreatment device water inlet and a pretreatment device dosing port which are arranged on the pretreatment device tank body, a pretreatment device supernatant outlet which is arranged on the pretreatment device tank body and is positioned on one side opposite to the pretreatment device water inlet, and a pretreatment device sludge outlet which is arranged at the bottom of the pretreatment device tank body, wherein the pretreatment device dosing port is used for adding a medicament which enables calcium and magnesium ions in the incoming water to form precipitate, and the pretreatment device tank body is used for realizing coagulating sedimentation;
the sodium chloride crystallization system comprises a filtering device, a nanofiltration salt separation device, a concentration device and a crystallization device which are connected in sequence;
the filtering device comprises a filtering device body, a filtering device water inlet pipe arranged at one end of the filtering device body, a filtering device water outlet arranged on the filtering device body and opposite to the filtering device water inlet pipe, and a filtering device dosing part arranged on the filtering device water inlet pipe;
the nanofiltration salt separation device comprises a nanofiltration salt separation device body, a nanofiltration salt separation device water inlet arranged at one end of the nanofiltration salt separation device body, a nanofiltration salt separation device thick water inlet arranged at the other side of the nanofiltration salt separation device body and a nanofiltration salt separation device water outlet;
the concentration device comprises a concentration device body, a concentration device water inlet arranged on one side of the concentration device body, a concentration device water inlet arranged on the other side of the concentration device body and a concentration device water outlet;
the crystallization device comprises a crystallization device body, a crystallization device liquid inlet, a crystallization device mother liquid outlet and a crystallization device discharge port, wherein the crystallization device liquid inlet, the crystallization device mother liquid outlet and the crystallization device discharge port are arranged on the crystallization device body;
the supernatant fluid outlet of the pretreatment device is connected with the water inlet pipe of the filter device, the water outlet of the filter device is connected with the water inlet of the nanofiltration salt separation device, and the water outlet of the nanofiltration salt separation device is connected with the water inlet of the concentration device; the concentrated water port of the concentration device is connected with the liquid inlet of the crystallization device; the filtering device dosing part is used for dosing a second medicament:
the filtering device is used for precipitating calcium ions remained in the supernatant by adding a second medicament and filtering to remove the calcium ions to obtain a clarified liquid, and the nano-filtration salt separating device is used for separating monovalent ions and divalent ions in the clarified liquid to obtain sodium chloride water; the concentration device is used for concentrating the sodium chloride produced water to obtain a sodium chloride concentrated solution; the crystallizing device is used for obtaining sodium chloride crystals from the sodium chloride concentrated solution, and a discharge port of the crystallizing device is used for discharging the sodium chloride crystals;
the magnesium sulfate crystallization system comprises a sludge dehydration device, a heating device, a secondary dehydration device, a second concentration device and a second crystallization device which are connected in sequence;
the sludge dewatering device comprises a sludge dewatering device body, a sludge inlet of the sludge dewatering device arranged on one side of the sludge dewatering device body, a liquid outlet of the sludge dewatering device arranged on the other side of the sludge dewatering device body and a sludge outlet of the sludge dewatering device;
the heating device comprises a heating device body, a heating device mud inlet and a heating device medicine adding part which are arranged on the heating device body, and a heating device liquid outlet which is arranged on the heating device body and is positioned on one side opposite to the heating device mud inlet;
the secondary dehydration device comprises a secondary dehydration device body, a secondary dehydration device water inlet arranged at one side of the secondary dehydration device body, a secondary dehydration device liquid outlet arranged at the other side of the secondary dehydration device body and a secondary dehydration device dry mud discharge port;
the second concentration device comprises a second concentration device body, a second concentration device water inlet arranged on one side of the second concentration device body, and a second concentration device water inlet arranged on the side, opposite to the second concentration device water inlet, of the second concentration device body;
the second crystallization device comprises a second crystallization device body, a second crystallization device liquid inlet, a second crystallization device mother liquid outlet and a second crystallization device discharge port, wherein the second crystallization device liquid inlet, the second crystallization device mother liquid outlet and the second crystallization device discharge port are arranged on the second crystallization device body;
a sludge inlet of the sludge dewatering device is connected with a sludge outlet of the pretreatment device, a sludge inlet of the heating device is connected with a sludge outlet of the sludge dewatering device, a liquid outlet of the heating device is connected with a water inlet of the secondary dewatering device, a liquid outlet of the secondary dewatering device is connected with a water inlet of the second concentration device, and a concentrated water outlet of the second concentration device is connected with a liquid inlet of the second crystallization device; the heating device dosing part is used for dosing a third medicament;
the sludge dewatering device is used for dewatering the sludge discharged by the pretreatment device, and the heating device is used for controlling the temperature and the pH value of the sludge and precipitating magnesium ions under the action of a third agent to generate magnesium sulfate and obtain a magnesium sulfate solution; the secondary dehydration device is used for removing calcium sulfate precipitate in the magnesium sulfate solution and discharging the calcium sulfate precipitate from a dry sludge discharge port of the secondary dehydration device; the second concentration device is used for obtaining magnesium sulfate concentrated solution; the second crystallizing device is used for obtaining magnesium sulfate crystals from the magnesium sulfate concentrated solution; and the discharge port of the second crystallizing device is used for discharging magnesium sulfate crystals.
The system for extracting the magnesium sulfate and the sodium chloride from the desulfurization wastewater is characterized in that as a preferred mode, an adjusting tank is further arranged at the water inlet end of the pretreatment device, and comprises an adjusting tank body, an adjusting tank water inlet pipe arranged on the adjusting tank body, and an adjusting tank water outlet arranged on the adjusting tank body and located on the opposite side of the adjusting tank water inlet pipe;
the water inlet pipe of the regulating reservoir is connected with the incoming water of the desulfurization wastewater, the water outlet of the regulating reservoir is connected with the water inlet of the pretreatment device, and the desulfurization wastewater enters the pretreatment device after passing through the regulating reservoir;
the concentrated water port of the nanofiltration salt separation device is connected with the water inlet pipe of the regulating tank.
As an optimal mode, a liquid outlet of the sludge dewatering device is connected with a water inlet pipe of the regulating tank.
As an optimal mode, the mother liquor outlet of the second crystallization device is connected with the sludge inlet of the heating device.
According to the system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, as a preferred mode, a medicament added at a medicament adding port of a pretreatment device is calcium hydroxide; the sediment discharged from the sludge discharge port is magnesium hydroxide and calcium sulfate; the second agent added by the dosing part of the filtering device is sodium carbonate, so that calcium ions remained in the supernatant generate calcium carbonate precipitate and are filtered and removed; the third agent added by the medicine adding part of the heating device is sulfuric acid.
The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater provided by the invention has the advantages that as an optimal mode, the pool body is a high-density sedimentation pool or a mechanical accelerated clarification pool, the filtering device is a tubular membrane filtering device, the tubular membrane filtering device adopts a tubular ultrafiltration membrane or a tubular microfiltration membrane, and the membrane pores are 0.05-0.2 um;
the concentration device is a high-pressure membrane concentration device which uses a high-pressure roll membrane or a DTRO disc tube type reverse osmosis membrane;
the crystallization device is an MVR mechanical vapor recompression device;
the sludge dewatering device is a centrifugal dewatering machine;
the secondary dewatering device is a plate-and-frame filter press;
the second concentration device is an evaporation concentration device;
the second crystallization apparatus is a freeze crystallization apparatus.
The invention provides a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, which comprises the following steps:
s1, adding a medicament from a medicament adding port of a pretreatment device after desulfurization wastewater enters the pretreatment device to obtain calcium and magnesium ion precipitate and supernatant;
s2, enabling the supernate to enter a sodium chloride crystallization system through a supernate outlet of a pretreatment device, removing residual calcium ions from the supernate under the action of a second agent added into a water inlet pipe of a filtering device, filtering the supernate by using the filtering device to obtain a filtrate, enabling the filtrate to enter a nanofiltration salt separation device to separate monovalent ions and divalent ions to obtain sodium chloride produced water, concentrating the sodium chloride produced water by using a concentrating device to obtain a sodium chloride concentrated solution, and enabling the sodium chloride concentrated solution to obtain sodium chloride crystals under the action of a crystallizing device;
s3, enabling a sludge discharge port of a pretreatment device for calcium and magnesium ion precipitation to enter a magnesium sulfate crystallization system, dehydrating the sludge through a sludge and sludge dehydration device, enabling the sludge and sludge dehydration device to enter a sludge heating device, generating magnesium sulfate under the action of a third agent through magnesium ion precipitation in the sludge heating device, obtaining a magnesium sulfate solution and calcium sulfate precipitation, dehydrating the sludge through a secondary dehydration device, concentrating the magnesium sulfate solution through a second concentration device, and obtaining magnesium sulfate crystals through the magnesium sulfate concentrated solution under the action of the second crystallization device; the calcium sulfate precipitate is discharged through a dry sludge discharge port of the secondary dewatering device.
In the method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, as a preferred mode, in the step S1, the desulfurization wastewater passes through the regulating tank before entering the pretreatment device;
and (S2) returning the concentrated water of the nano-filtration salt separation device to the regulating tank for regulating and homogenizing, and then continuing to enter a sodium chloride crystallization system and a magnesium sulfate crystallization system.
In the method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, as a preferred mode, in the step S3, the discharged liquid of the liquid outlet of the sludge dewatering device flows back to the regulating tank for regulating and homogenizing, and then continuously enters the sodium chloride crystallization system and the magnesium sulfate crystallization system; and the mother liquor discharged from the mother liquor outlet of the second crystallizing device in the step S3 flows back to the sludge inlet of the heating device.
In the method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater, as a preferred mode, the medicament in the step S1 is calcium hydroxide; the magnesium ion precipitate is magnesium hydroxide, and meanwhile, calcium sulfate precipitate is obtained; step S2, the second agent is sodium carbonate, so that calcium ion remained in the supernatant is precipitated into calcium carbonate and filtered to remove it; the third agent in step S3 is sulfuric acid, which precipitates magnesium hydroxide to form magnesium sulfate.
In the pretreatment device, a medicament (calcium hydroxide) is added to soften and precipitate calcium and magnesium ions, and at the pH value of about 11.3, most of the calcium and magnesium ions are finally discharged out of the pretreatment device in the form of sludge, and calcium sulfate precipitation is generated at the same time. The supernatant discharged from the supernatant discharge port enters a filtering device, and the sludge discharged from the sludge discharge port enters a sludge dewatering device.
The filtering device is mainly used for removing residual calcium ions and retaining non-precipitated particulate matters in the pretreatment softening system. The second agent (sodium carbonate) is added into the water inlet pipe of the filtering device, so that calcium ions remained in the supernatant liquid are generated into calcium carbonate and filtered to be removed. The filtering device is generally a tubular membrane filtering device, and a tubular ultrafiltration membrane or a tubular microfiltration membrane is usually adopted, and the membrane pore diameter is often 0.05um to 0.2 um. The tubular membrane can continuously operate under the condition of high pH (the pH is more than 10), and can ensure that calcium, magnesium and silicon precipitates and ion components with scaling tendency such as strontium, barium and the like can be effectively removed, so that the calcium and magnesium ion components in the produced water of the tubular membrane are usually less than 20ppm, and the turbidity of the produced water is less than 1.0 NTU. And the produced water of the tubular membrane filtering device enters a nano-filtration salt separating device.
The nanofiltration salt separation device mainly realizes the separation of monovalent ions and divalent ions through the unique characteristic of a nanofiltration membrane, and the main components in nanofiltration produced water are monovalent ions, such as sodium ions, chloride ions and the like. The main component of the nanofiltration concentrated water is divalent ions, such as calcium, magnesium ions, sulfate ions and the like. And (4) refluxing the nanofiltration concentrated water to an inlet of the regulating tank. And the produced water of the nanofiltration salt separation device enters a concentration device.
The concentration device is generally a high-pressure membrane concentration device, and concentrated water of the high-pressure membrane concentration device enters an inlet of the crystallization device through a concentrated water inlet. The water produced by high-pressure membrane concentration is purified water, and can be recycled in a factory.
The sodium chloride crystallization device is generally an evaporative crystallization device and comprises a liquid inlet, evaporative crystallization equipment, a sodium chloride crystallized salt discharge port, a sodium chloride mother liquid port and a noncondensable gas discharge port. And discharging the sodium chloride mother liquor of the evaporative crystallization device after drying treatment. The principle of the evaporative crystallization technique is "the continuous decrease of the solvent → the increase of the concentration → the reaching of the saturated concentration → the crystallization". The sodium chloride crystal salt is discharged from a discharge port of the sodium chloride evaporation crystallization device, can be sold for take-out, and realizes resource utilization of sodium chloride industrial salt. The sodium chloride evaporative crystallization device usually adopts MVR mechanical vapor recompression equipment, and usually comprises a preheater, a heat exchanger, an evaporator, a centrifuge, a compressor, a crystallizer, a thickener and the like, wherein an incondensable gas discharge port discharges incondensable pure vapor to a safe position.
And the filtrate discharged from the liquid outlet of the sludge dewatering device flows back to the inlet of the pretreatment softening device. The sludge is dewatered and discharged from a sludge discharge port to enter a sludge inlet of the heating device. The sludge dewatering equipment generally employs a centrifugal dehydrator, and the water content of the dewatered sludge discharged from the sludge dewatering equipment is generally about 80%. The sludge dewatering device realizes the reduction treatment of the sludge amount.
In a heating device, controlling the pH value to be 5 and the temperature to be 80 ℃, and mixing a third agent (sulfuric acid) and Mg (OH) in the sludge2Reaction to form MgSO4The solution is discharged from the solution outlet of the heating device into a secondary dewatering device.
And carrying out external transportation treatment, such as landfill or drying, on the reduced dry mud discharged by the secondary dehydration device. The liquid outlet of the secondary dewatering device is connected with the inlet of the second concentration device. The main part of the secondary dewatering device is secondary dewatering equipment, and the solid-liquid separation of mud and water from the device is realized. The secondary dewatering equipment usually adopts a plate-and-frame filter press, and the water content of dry mud discharged by the secondary dewatering device is usually 65-70%.
The magnesium sulfate evaporation concentration device comprises a liquid inlet, evaporation concentration equipment and a liquid outlet. After evaporation concentration treatment, the effluent enters a second crystallization device.
The second crystallization apparatus is generally a freeze crystallization apparatus. The principle of the freeze crystallization technique is "temperature reduction → solubility reduction to the current solution concentration → crystallization. The magnesium sulfate crystal salt is discharged from the discharge port of the second crystallizing device, can be sold in a take-out way, and realizes resource utilization of the magnesium sulfate industrial salt. Further preferably, a part of the mother liquor in the mother liquor of the second crystallization device can be refluxed to the heating device, and another small part of the mother liquor is discharged. The second crystallization apparatus generally comprises a crystallizer, a precooler and the like.
The technological process of the invention is mainly divided into a sodium chloride production process and a magnesium sulfate production process.
1. The production process of sodium chloride comprises the following steps: after the water quality and the water quantity of the desulfurization wastewater are balanced by a regulating tank, the desulfurization wastewater enters a pretreatment device, the pretreatment device usually adopts a high-density sedimentation tank or a mechanical accelerated clarification tank and the like, and a softening agent calcium hydroxide is added into the pretreatment device to form Mg (OH)2And CaSO4And (3) precipitating, enabling supernatant of the pretreatment device to enter a filtering device to remove residual calcium ions and filtering, enabling produced water of the filtering device to enter a nano-filtration salt separation device to realize salt separation (the divalent ion separation removal rate is up to more than 98%), and enabling the produced water to be rich in Na+And Cl-The nanofiltration water produced by the monovalent ions enters a subsequent concentration device for concentration and decrement, the fresh water of the concentration device is recycled, the concentrated water of the concentration device enters a crystallization device for evaporation and crystallization, an evaporation and crystallization system produces sodium chloride industrial salt, the product purity is higher than 97.5 percent, and the product reaches the secondary standard of refined industrial salt specified in the GB/T5462-2016 industrial salt standard.
2. The production process of magnesium sulfate comprises the following steps: pretreatment of the Mg (OH) formed by the softening units2And CaSO4When the sludge is precipitated, the sludge is firstly dewatered and reduced, and centrifugal dewatering is generally adoptedThe water machine and other equipment reduce the water content of the sludge, filtrate flows back to the regulating tank, and the dewatered sludge enters the heating device. In a heating device, the dewatered sludge and a third medicament (sulfuric acid) are fully reacted at a certain temperature (80 ℃) to ensure that Mg (OH) in the sludge is reacted2Precipitation reaction to form MgSO4And (4) forming a mud-water mixed solution. And then, the mud-water mixed solution enters a secondary dehydration device, a plate-and-frame filter press is adopted to dehydrate the mud-water mixed solution again, mud cakes generated by the plate-and-frame filter press are transported outwards, and filtrate generated by the plate-and-frame filter press is high-concentration magnesium sulfate solution. The magnesium sulfate solution is further subjected to freezing crystallization after being evaporated and concentrated, and the magnesium sulfate crystal salt is generated through freezing crystallization, the product purity is higher than 98 percent and reaches the qualified standard of magnesium sulfate heptahydrate class I of HG/T2680-2017 Industrial magnesium sulfate.
The invention has the advantages that:
(1) can maximally recover inorganic salt in the desulfurization wastewater, increase resource recovery and reduce the discharged sludge amount. In general desulfurization wastewater, the main salt component is Na+、Cl-、Mg2+、SO4 2-The method simultaneously recovers magnesium sulfate and sodium chloride in the desulfurization wastewater, can recover most inorganic salts, and realizes decrement treatment of solid wastes and resource recycling.
(2) Wide application range and can adapt to the desulfurization waste water with various water qualities. The desulfurization waste water is different from the desulfurization limestone components according to the quality of the fire coal used by each power plant, and the proportion of various ions is greatly different.
(3) The system runs stably and reliably. The main units of the sodium chloride production process are all positioned in the subsequent unit of the water production of the nanofiltration membrane, and the magnesium sulfate production process greatly avoids the influence of organic matters and scaling ions in water through sludge dehydration → redissolution reaction → sludge secondary dehydration, so that the operation is more stable and reliable.
(4) Furthermore, because about 50% of magnesium ions and sulfate ions exist in the magnesium sulfate freezing crystallization mother liquor, part of the magnesium sulfate mother liquor flows back to the heating reaction device, so that the extraction of magnesium sulfate in the desulfurization waste water can be realized to the maximum extent, and in addition, potassium ions, nitrate ions, COD (chemical oxygen demand) and the like in the magnesium sulfate mother liquor can be discharged from the system disclosed by the invention through discharge.
(5) Among other patent process technologies, there is a process for decomposing mirabilite into sodium hydroxide and sulfuric acid through a bipolar membrane unit, and the patent technology is characterized in that sodium ions in mirabilite are introduced, so that the content of sodium ions in a subsequent treatment unit TDS (total soluble solid matter) is increased, and the operation cost and energy consumption of a subsequent system are increased. This patent technique adopts softening agent to be calcium hydroxide, and the calcium ion reacts with the sulfate radical in the desulfurization waste water and generates calcium sulfate sediment, turns into mud. The hydroxide radical and magnesium ion are combined to react to generate magnesium hydroxide precipitate, and finally the magnesium hydroxide reacts with sulfuric acid to generate magnesium sulfate and water. The treatment process does not increase the content of sodium ions in TDS (total soluble solid matter) of the subsequent treatment process, so the finishing operation cost and the energy consumption are lower.
(6) Compared with the method for forming the magnesium sulfate crystal by direct nanofiltration treatment, the method for forming the magnesium sulfate crystal by precipitation separation of magnesium ions has the following beneficial effects:
firstly, when the nano-filtration separation is directly carried out, a special selective calcium remover is needed to be adopted to precipitate and remove calcium ions in the wastewater and retain magnesium ions, and the special selective calcium remover has high cost (10000 yuan/ton) and high operation cost (30-40 yuan/ton water).
Adopting a calcium-magnesium ion precipitation separation method, wherein the components in the precipitated sludge are magnesium hydroxide and calcium sulfate, and Ca (OH) is adopted2As a precipitating agent, Mg (OH) therein is then dissolved with sulfuric acid2Magnesium sulfate solution is formed, the medicament is common, and the operation cost is low;
secondly, when the nanofiltration membrane is directly separated, because the selective calcium remover is added in the water inlet process of nanofiltration, the solution is in a calcium ion saturated state while calcium ions are precipitated, and in the nanofiltration concentrated water, the calcium saturated solution is easy to precipitate to form salt scale to be deposited on the surface of the nanofiltration membrane, thereby reducing the separation performance and the service life of the nanofiltration membrane.
And thirdly, in the nanofiltration membrane separation technology, the residual amount of magnesium ions in the nanofiltration water is more and about 20 percent of the concentration of the magnesium ions in the nanofiltration water, and the magnesium ions enter the subsequent sodium chloride evaporation crystallization process, so that the residual amount of the magnesium ions is more, the amount of sodium chloride mother liquor is increased, and the yield of sodium chloride crystal salt is reduced.
Therefore, the process technology of the invention has wide application prospect.
Drawings
FIG. 1 is a diagram of a system and a method for extracting magnesium sulfate and sodium chloride from desulfurization waste water, and a device in embodiment 1 of the method;
FIG. 2 is a diagram of a device in embodiment 2 of a system and a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater;
FIG. 3 is a diagram of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water, in an embodiment 3;
FIG. 4 is a diagram of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water, and a device in embodiment 4;
FIG. 5 is a diagram of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water, and the device of embodiment 7;
FIG. 6 is a flow chart of an embodiment 8 of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water;
FIG. 7 is a flow chart of an embodiment 9 of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water;
FIG. 8 is a flow chart of an embodiment 10 of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water;
FIG. 9 is a flow chart of an embodiment 11 of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water;
FIG. 10 is a flow chart of a system and method for extracting magnesium sulfate and sodium chloride from desulfurization waste water in an embodiment 12.
Reference numerals:
1. a pretreatment device; 11. a pretreatment device pool body; 12. a water inlet of the pretreatment device; 13. a dosing port of the pretreatment device; 14. a pre-treatment device supernatant outlet; 15. a sludge discharge port of the pretreatment device; 2. a sodium chloride crystallization system; 21. a filtration device; 211. a filter device body; 212. a water inlet pipe of the filtering device; 213. a water outlet of the filtering device; 214. a filtering device dosing part; 22. a nanofiltration salt separation device; 221. a nanofiltration salt separation device body; 222. a water inlet of the nanofiltration salt separation device; 223. a concentrated water port of the nanofiltration salt separation device; 224. a water producing port of the nanofiltration salt separating device; 23. a concentration device; 231. a concentration device body; 232. a water inlet of the concentration device; 233. a concentrated water port of the concentration device; 234. a water producing port of the concentration device; 24. a crystallization device; 241. a crystallization apparatus body; 242. a liquid inlet of a crystallization device; 243. a mother liquor outlet of the crystallization device; 244. a discharge port of the crystallization device; 3. a magnesium sulfate crystallization system; 31. a sludge dewatering device; 311. a sludge dewatering device body; 312. a sludge inlet of the sludge dewatering device; 313. a liquid outlet of the sludge dewatering device; 314. a sludge discharge port of the sludge dewatering device; 32. a warming device; 321. a warming device body; 322. a mud inlet of the heating device; 323. a heating device dosing part; 324. a liquid outlet of the heating device; 33. a secondary dewatering device; 331. a secondary dewatering device body; 332. a water inlet of the secondary dewatering device; 333. a liquid outlet of the secondary dewatering device; 334. a dry sludge discharge port of the secondary dewatering device; 34. a second concentration device; 341. a second concentrator body; 342. a water inlet of a second concentration device; 343. a second concentrator concentrate port; 35. a second crystallization device; 351. comprises a second crystallizing device body; 352 liquid inlet of a second crystallization device; 353. a mother liquor outlet of the second crystallization device; 354. a discharge port of a second crystallization device; 4. a regulating tank; 41. a regulating reservoir body; 42. a regulating reservoir water inlet pipe; 43. and a water outlet of the regulating tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
As shown in fig. 1, a system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater comprises a pretreatment device 1, a sodium chloride crystallization system 2 and a magnesium sulfate crystallization system 3, wherein the sodium chloride crystallization system 2 and the magnesium sulfate crystallization system 3 are respectively connected with the pretreatment device 1;
the pretreatment device 1 comprises a pretreatment device tank body 11, a pretreatment device water inlet 12 and a pretreatment device chemical feeding port 13 which are arranged on the pretreatment device tank body 11, a pretreatment device supernatant outlet 14 which is arranged on one side of the pretreatment device tank body 11 opposite to the pretreatment device water inlet 12 and a pretreatment device sludge outlet 15 which is arranged at the bottom of the pretreatment device tank body 11, wherein the pretreatment device chemical feeding port 13 is used for feeding a chemical which enables calcium and magnesium ions in incoming water to form precipitate, and the pretreatment device tank body 11 is used for realizing coagulating sedimentation;
the sodium chloride crystallization system 2 comprises a filtering device 21, a nano-filtration salt separation device 22, a concentration device 23 and a crystallization device 24 which are connected in sequence;
the filtering device 21 comprises a filtering device body 211, a filtering device water inlet pipe 212 arranged at one end of the filtering device body 211, a filtering device water outlet 213 arranged at the opposite side of the filtering device water inlet pipe 212 on the filtering device body 211, and a filtering device medicine adding part 214 arranged on the filtering device water inlet pipe 212;
the nano-filtration salt separation device 22 comprises a nano-filtration salt separation device body 221, a nano-filtration salt separation device water inlet 222 arranged at one end of the nano-filtration salt separation device body 221, a nano-filtration salt separation device water concentrate inlet 223 arranged at the other side of the nano-filtration salt separation device body 221 and a nano-filtration salt separation device water production inlet 224;
the concentration device 23 comprises a concentration device body 231, a concentration device water inlet 232 arranged at one side of the concentration device body 231, a concentration device water outlet 233 arranged at the other side of the concentration device body 231 and a concentration device water outlet 234;
the crystallization device 24 comprises a crystallization device body 241, a crystallization device liquid inlet 242, a crystallization device mother liquid outlet 243 and a crystallization device discharge outlet 244 which are arranged on the crystallization device body 241;
the supernatant outlet 14 of the pretreatment device is connected with the water inlet pipe 212 of the filtration device, the water outlet 213 of the filtration device is connected with the water inlet 222 of the nano-filtration salt separation device, and the water outlet 224 of the nano-filtration salt separation device is connected with the water inlet 232 of the concentration device; the concentration device thick water port 233 is connected with the crystallization device liquid inlet 242; the filtering device dosing part 214 is used for dosing a second medicament:
the filtering device 21 precipitates calcium ions remained in the supernatant by adding a second medicament and removes the calcium ions by filtration to obtain a filtrate, and the nano-filtration salt separating device 22 is used for separating monovalent ions and divalent ions in the filtrate and obtaining sodium chloride water; the concentration device 23 is used for concentrating the sodium chloride produced water to obtain a sodium chloride concentrated solution; the crystallizing device 24 is used for obtaining sodium chloride crystals from the sodium chloride concentrated solution, and a discharge port 244 of the crystallizing device is used for discharging the sodium chloride crystals;
the magnesium sulfate crystallization system 3 comprises a sludge dewatering device 31, a heating device 32, a secondary dewatering device 33, a second concentration device 34 and a second crystallization device 35 which are connected in sequence;
the sludge dewatering device 31 comprises a sludge dewatering device body 311, a sludge dewatering device inlet 312 arranged at one side of the sludge dewatering device body 311, a sludge dewatering device liquid outlet 313 arranged at the other side of the sludge dewatering device body 311 and a sludge dewatering device sludge outlet 314;
the heating device 32 comprises a heating device body 321, a heating device mud inlet 322 arranged on the heating device body 321, a heating device medicine adding component 323, and a heating device liquid outlet 324 arranged on the heating device body 321 and positioned on the opposite side of the heating device mud inlet 322;
the secondary dewatering device 33 comprises a secondary dewatering device body 331, a secondary dewatering device water inlet 332 arranged at one side of the secondary dewatering device body 331, a secondary dewatering device liquid outlet 333 arranged at the other side of the secondary dewatering device body 331 and a secondary dewatering device dry mud discharge outlet 334;
the second thickener 34 includes a second thickener body 341, a second thickener water inlet 342 provided at one side of the second thickener body 341, and a second thickener concentrate outlet 343 provided at the opposite side of the second thickener body 341 from the second thickener water inlet 342;
the second crystallization device 35 comprises a second crystallization device body 351, a second crystallization device liquid inlet 352, a second crystallization device mother liquid outlet 353 and a second crystallization device discharge outlet 354, which are arranged on the second crystallization device body 351;
the sludge inlet 312 of the sludge dewatering device is connected with the sludge outlet 15 of the pretreatment device, the sludge inlet 322 of the heating device is connected with the sludge outlet 314 of the sludge dewatering device, the liquid outlet 324 of the heating device is connected with the water inlet 332 of the secondary dewatering device, the liquid outlet 333 of the secondary dewatering device is connected with the water inlet 342 of the second concentration device, and the thick water outlet 343 of the second concentration device is connected with the liquid inlet 352 of the second crystallization device; the heating device dosing part 323 is used for dosing a third medicament;
the sludge dewatering device 31 is used for dewatering the sludge discharged by the pretreatment device 1, and the heating device 32 is used for controlling the temperature and the pH value of the sludge and precipitating magnesium ions under the action of a third agent to generate magnesium sulfate and obtain a magnesium sulfate solution; the secondary dewatering device 33 is used for removing calcium sulfate precipitate in the magnesium sulfate solution and discharging the calcium sulfate precipitate from a dry sludge discharge port 334 of the secondary dewatering device; the second concentration device 34 is used for obtaining magnesium sulfate concentrated solution; the second crystallizing device 35 is used for obtaining magnesium sulfate crystals from the magnesium sulfate concentrated solution; the second crystallizer discharge port 354 is used for discharging magnesium sulfate crystals.
Example 2
As shown in fig. 2, on the basis of embodiment 1, a regulating reservoir 4 is further disposed at the water inlet end of the pretreatment device 1, and the regulating reservoir 4 includes a regulating reservoir body 41, a regulating reservoir water inlet pipe 42 disposed on the regulating reservoir body 41, and a regulating reservoir water outlet 43 disposed on the regulating reservoir body 41 and located on the opposite side of the regulating reservoir water inlet pipe 42;
the adjusting tank water inlet pipe 42 is connected with the incoming water of the desulfurization wastewater, the adjusting tank water outlet 43 is connected with the pretreatment device water inlet 12, and the desulfurization wastewater enters the pretreatment device 1 after passing through the adjusting tank 4;
the concentrated water port 223 of the nano-filtration salt separation device is connected with the water inlet pipe 42 of the adjusting tank.
Example 3
As shown in FIG. 3, in example 2, the drain port 313 of the sludge dewatering device was connected to the inlet pipe 42 of the adjustment tank.
Example 4
As shown in FIG. 4, in example 2, the mother liquor outlet 353 of the second crystallization device is connected to the sludge inlet 322 of the warming device.
Example 5
As shown in fig. 1, on the basis of example 1, the agent added by the dosing port 13 of the pretreatment device is calcium hydroxide; the sediment discharged from the sludge discharge port 15 is magnesium hydroxide and calcium sulfate; the second agent added by the medicine adding part 214 of the filtering device is sodium carbonate, so that calcium ions remained in the supernatant generate calcium carbonate precipitate and are filtered and removed; the third agent added by the medicine adding part 323 of the heating device is sulfuric acid.
Example 6
As shown in fig. 1, on the basis of example 1, the tank body 11 is a high-density sedimentation tank or a mechanical accelerated clarification tank, the filtering device 21 is a tubular membrane filtering device, the tubular membrane filtering device adopts a tubular ultrafiltration membrane or a tubular microfiltration membrane, and the membrane pores are 0.05um to 0.2 um;
the concentration device 23 is a high-pressure membrane concentration device using a high-pressure roll membrane or a DTRO disc tube type reverse osmosis membrane;
the sludge dewatering device 31 is a centrifugal dewatering machine;
the secondary dewatering device 33 is a plate-and-frame filter press;
the second concentration device 34 is an evaporation concentration device;
the second crystallization device 35 is a freezing crystallization device.
Example 7
As shown in fig. 5, as shown in fig. 1, a system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater comprises a pretreatment device 1, a sodium chloride crystallization system 2 and a magnesium sulfate crystallization system 3 which are respectively connected with the pretreatment device 1, and an adjusting tank 4 is further arranged at a water inlet end of the pretreatment device 1;
the pretreatment device 1 comprises a pretreatment device tank body 11, the tank body 11 is a high-density sedimentation tank or a mechanical accelerated clarification tank, a pretreatment device water inlet 12 and a pretreatment device dosing port 13 are arranged on the pretreatment device tank body 11, a pretreatment device supernatant discharge port 14 and a pretreatment device sludge discharge port 15 are arranged on the pretreatment device tank body 11 and are positioned on one side opposite to the pretreatment device water inlet 12, the pretreatment device sludge discharge port 13 is used for adding a medicament (calcium hydroxide) which enables calcium and magnesium ions in the incoming water to form magnesium hydroxide and calcium sulfate precipitates, the pH value in the pretreatment device is about 11.3, and the pretreatment device tank body 11 is used for realizing coagulation and precipitation;
the sodium chloride crystallization system 2 comprises a filtering device 21, a nano-filtration salt separation device 22, a concentration device 23 and a crystallization device 24 which are connected in sequence;
the filtering device 21 comprises a filtering device body 211, a filtering device water inlet pipe 212 arranged at one end of the filtering device body 211, a filtering device water outlet 213 arranged at the opposite side of the filtering device water inlet pipe 212 on the filtering device body 211, and a filtering device medicine adding part 214 arranged on the filtering device water inlet pipe 212; the filtering device 21 is a tubular membrane filtering device which adopts a tubular ultrafiltration membrane or a tubular microfiltration membrane, and the membrane pores are 0.05 um-0.2 um;
the nano-filtration salt separation device 22 comprises a nano-filtration salt separation device body 221, a nano-filtration salt separation device water inlet 222 arranged at one end of the nano-filtration salt separation device body 221, a nano-filtration salt separation device water concentrate inlet 223 arranged at the other side of the nano-filtration salt separation device body 221 and a nano-filtration salt separation device water production inlet 224;
the concentration device 23 comprises a concentration device body 231, a concentration device water inlet 232 arranged at one side of the concentration device body 231, a concentration device water outlet 233 arranged at the other side of the concentration device body 231 and a concentration device water outlet 234; the concentration device 23 is a high-pressure membrane concentration device using a high-pressure roll membrane or a DTRO disc tube type reverse osmosis membrane;
the crystallization device 24 comprises a crystallization device body 241, a crystallization device liquid inlet 242, a crystallization device mother liquid outlet 243 and a crystallization device discharge outlet 244 which are arranged on the crystallization device body 241; crystallization device 24 is an MVR mechanical vapor recompression device;
the supernatant outlet 14 of the pretreatment device is connected with the water inlet pipe 212 of the filtration device, the water outlet 213 of the filtration device is connected with the water inlet 222 of the nano-filtration salt separation device, and the water outlet 224 of the nano-filtration salt separation device is connected with the water inlet 232 of the concentration device; the concentration device thick water port 233 is connected with the crystallization device liquid inlet 242; the filtering device dosing part 214 is used for dosing a second medicament:
a filtering device 21 for precipitating calcium ions remained in the supernatant by adding a second medicament (sodium carbonate) and filtering to remove the calcium ions to obtain a filtrate, and a nano-filtration salt separating device 22 for filtering monovalent ions and divalent ions in the clarified solution to obtain sodium chloride water; the concentration device 23 is used for concentrating the sodium chloride produced water to obtain a sodium chloride concentrated solution; the crystallizing device 24 is used for obtaining sodium chloride crystals from the sodium chloride concentrated solution, and a discharge port 244 of the crystallizing device is used for discharging the sodium chloride crystals;
the magnesium sulfate crystallization system 3 comprises a sludge dewatering device 31, a heating device 32, a secondary dewatering device 33, a second concentration device 34 and a second crystallization device 35 which are connected in sequence;
the sludge dewatering device 31 comprises a sludge dewatering device body 311, a sludge dewatering device inlet 312 arranged at one side of the sludge dewatering device body 311, a sludge dewatering device liquid outlet 313 arranged at the other side of the sludge dewatering device body 311 and a sludge dewatering device sludge outlet 314; the sludge dewatering device 31 is a centrifugal dewatering machine;
the heating device 32 comprises a heating device body 321, a heating device mud inlet 322 arranged on the heating device body 321, a heating device medicine adding component 323, and a heating device liquid outlet 324 arranged on the heating device body 321 and positioned on the opposite side of the heating device mud inlet 322; controlling the pH value to be 5 and the temperature to be 80 ℃ in a heating device;
the secondary dewatering device 33 comprises a secondary dewatering device body 331, a secondary dewatering device water inlet 332 arranged at one side of the secondary dewatering device body 331, a secondary dewatering device liquid outlet 333 arranged at the other side of the secondary dewatering device body 331 and a secondary dewatering device dry mud discharge outlet 334; the secondary dewatering device 33 is a plate-and-frame filter press;
the second thickener 34 includes a second thickener body 341, a second thickener water inlet 342 provided at one side of the second thickener body 341, and a second thickener concentrate outlet 343 provided at the opposite side of the second thickener body 341 from the second thickener water inlet 342; the second concentration device 34 is an evaporation concentration device;
the second crystallization device 35 comprises a second crystallization device body 351, a second crystallization device liquid inlet 352, a second crystallization device mother liquid outlet 353 and a second crystallization device discharge outlet 354, which are arranged on the second crystallization device body 351; the second crystallization device 35 is a freezing crystallization device.
The sludge inlet 312 of the sludge dewatering device is connected with the sludge outlet 15 of the pretreatment device, the sludge inlet 322 of the heating device is connected with the sludge outlet 314 of the sludge dewatering device, the liquid outlet 324 of the heating device is connected with the water inlet 332 of the secondary dewatering device, the liquid outlet 333 of the secondary dewatering device is connected with the water inlet 342 of the second concentration device, and the thick water outlet 343 of the second concentration device is connected with the liquid inlet 352 of the second crystallization device; the heating device dosing part 323 is used for dosing a third medicament (sulfuric acid);
the sludge dewatering device 31 is used for dewatering the sludge discharged by the pretreatment device 1, and the heating device 32 is used for controlling the temperature and the pH value of the sludge and precipitating magnesium ions under the action of a third agent to generate magnesium sulfate and obtain a magnesium sulfate solution; the secondary dewatering device 33 is used for removing calcium sulfate precipitate in the magnesium sulfate solution and discharging the calcium sulfate precipitate from a dry sludge discharge port 334 of the secondary dewatering device; the second concentration device 34 is used for obtaining magnesium sulfate concentrated solution; the second crystallizing device 35 is used for obtaining magnesium sulfate crystals from the magnesium sulfate concentrated solution; the second crystallizer discharge port 354 is used for discharging magnesium sulfate crystals.
The adjusting tank 4 comprises an adjusting tank body 41, an adjusting tank water inlet pipe 42 arranged on the adjusting tank body 41, and an adjusting tank water outlet 43 arranged on the adjusting tank body 41 and positioned on one side opposite to the adjusting tank water inlet pipe 42;
the adjusting tank water inlet pipe 42 is connected with the incoming water of the desulfurization wastewater, the adjusting tank water outlet 43 is connected with the pretreatment device water inlet 12, and the desulfurization wastewater enters the pretreatment device 1 after passing through the adjusting tank 4;
the liquid outlet 313 of the sludge dewatering device is connected with the water inlet pipe 42 of the adjusting tank;
the mother liquor outlet 353 of the second crystallization device is connected with the sludge inlet 322 of the heating device;
the method of use of examples 1-7 was: 1. the production flow of sodium chloride crystallization is as follows: the desulfurization wastewater enters a pretreatment device after the water quality and the water quantity are balanced by a regulating tank, the pretreatment device usually adopts a high-density sedimentation tank or a mechanical accelerated clarification tank and the like,adding softening agent calcium hydroxide into the pretreatment device to form Mg (OH)2And CaSO4Precipitating, filtering supernatant of the pretreatment device in a filtering device to remove residual calcium ions, separating salt (the divalent ion separation removal rate is up to more than 98%) by a nanofiltration salt separation device, and separating Na-rich water+And Cl-The nanofiltration water produced by the monovalent ions enters a subsequent concentration device for concentration and decrement, the fresh water of the concentration device is recycled, the concentrated water of the concentration device enters a crystallization device for evaporation and crystallization, an evaporation and crystallization system produces sodium chloride industrial salt, the product purity is higher than 97.5 percent, and the product reaches the secondary standard of refined industrial salt specified in the GB/T5462-2016 industrial salt standard.
2. Magnesium sulfate crystallization production process: pretreatment of the Mg (OH) formed by the softening units2And CaSO4When the sludge is precipitated, firstly, the sludge is dewatered and reduced, generally, equipment such as a centrifugal dehydrator is adopted to reduce the water content of the sludge, filtrate flows back to a regulating tank, and the dewatered sludge enters a heating device. In a heating device, the dewatered sludge and a third medicament (sulfuric acid) are fully reacted at a certain temperature (80 ℃) to ensure that Mg (OH) in the sludge is reacted2Precipitation reaction to form MgSO4And (4) forming a mud-water mixed solution. And then, the mud-water mixed solution enters a secondary dehydration device, a plate-and-frame filter press is adopted to dehydrate the mud-water mixed solution again, mud cakes generated by the plate-and-frame filter press are transported outwards, and filtrate generated by the plate-and-frame filter press is high-concentration magnesium sulfate solution. The magnesium sulfate solution is further subjected to freezing crystallization after being evaporated and concentrated, and the magnesium sulfate crystal salt is generated through freezing crystallization, the product purity is higher than 98 percent and reaches the qualified standard of magnesium sulfate heptahydrate class I of HG/T2680-2017 Industrial magnesium sulfate.
Example 8
As shown in fig. 6, a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater comprises the following steps:
s1, after desulfurization wastewater enters a pretreatment device 1, adding a medicament from a medicament adding port 13 of the pretreatment device to obtain calcium and magnesium ion precipitate and supernatant;
s2, enabling the supernate to enter a sodium chloride crystallization system 2 through a supernate outlet 14 of the pretreatment device, removing residual calcium ions from the supernate under the action of a second medicament added into a water inlet pipe 214 of a filtering device, filtering the supernate by the filtering device 2 to obtain a filtrate, enabling the filtrate to enter a nano-filtration salt separation device 22 to separate monovalent ions and divalent ions to obtain sodium chloride produced water, concentrating the sodium chloride produced water by a concentration device 23 to obtain a sodium chloride concentrated solution, and enabling the sodium chloride concentrated solution to obtain sodium chloride crystals under the action of a crystallization device 24;
s3, enabling the calcium and magnesium ion precipitate to pass through a sludge discharge port 15 of a pretreatment device to enter a magnesium sulfate crystallization system 3, dehydrating the calcium and magnesium ion precipitate through a sludge dehydration device 31, enabling the calcium and magnesium ion precipitate to enter a sludge heating device 32, generating magnesium sulfate under the action of a third agent in the sludge heating device 32 to obtain a magnesium sulfate solution and a calcium sulfate precipitate, dehydrating the magnesium sulfate solution through a secondary dehydration device 33, concentrating the magnesium sulfate solution through a second concentration device 34 to obtain a magnesium sulfate concentrated solution, and enabling the magnesium sulfate concentrated solution to obtain magnesium sulfate crystals under the action of a second crystallization device 35; the calcium sulfate precipitate is discharged through a secondary dewatering device dry sludge discharge port 334.
Example 9
As shown in FIG. 7, the basic method is the same as that of example 8, and in particular, the desulfurized wastewater in step S1 is passed through the conditioning tank 4 before entering the pretreatment apparatus 1;
the concentrated water of the nanofiltration salt separation device 22 in the step S2 flows back to the regulating tank 4 for regulating and homogenizing, and then continuously enters the sodium chloride crystallization system 2 and the magnesium sulfate crystallization system 3.
Example 10
As shown in fig. 8, the basic method is the same as that of example 9, and particularly, in step S3, the discharged liquid from the discharge port 313 of the sludge dewatering device is returned to the adjusting tank 4 to be adjusted and homogenized, and then is continuously fed into the sodium chloride crystallization system 2 and the magnesium sulfate crystallization system 3; the mother liquor discharged from the mother liquor outlet 353 of the second crystallization device in the step S3 is refluxed to the sludge inlet 322 of the heating device.
Example 11
As shown in fig. 9, the basic method is the same as in example 8, and in particular, the pharmaceutical agent in step S1 is calcium hydroxide; the magnesium ion precipitate is magnesium hydroxide, and meanwhile, calcium sulfate precipitate is obtained; step S2, the second agent is sodium carbonate, so that calcium ion remained in the supernatant is precipitated into calcium carbonate and filtered to remove it; the third agent in step S3 is sulfuric acid, which precipitates magnesium hydroxide to form magnesium sulfate.
Example 12
As shown in fig. 10, a method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater comprises the following steps:
s1, after desulfurization wastewater firstly passes through an adjusting tank 4 and then enters a pretreatment device 1, adding calcium hydroxide from a dosing port 13 of the pretreatment device to obtain magnesium hydroxide, calcium sulfate precipitate and supernatant;
s2, enabling the supernate to enter a sodium chloride crystallization system 2 through a supernate outlet 14 of a pretreatment device, removing residual calcium ions from the supernate under the action of sodium carbonate added into a water inlet pipe 214 of a filtering device, filtering the supernate by the filtering device 2 to obtain a filtrate, enabling the filtrate to enter a nano-filtration salt separation device 22 to separate monovalent ions and divalent ions to obtain sodium chloride produced water, concentrating the sodium chloride produced water by a concentration device 23 to obtain a sodium chloride concentrated solution, enabling the sodium chloride concentrated solution to obtain sodium chloride crystals under the action of a crystallization device 24, enabling concentrated water of the nano-filtration salt separation device 22 to flow back to a regulating tank 4 to be regulated and homogenized, and then continuing to enter the sodium chloride crystallization system 2 and a magnesium sulfate crystallization system 3;
s3, enabling the calcium and magnesium ion precipitate to pass through a sludge discharge port 15 of a pretreatment device to enter a magnesium sulfate crystallization system 3, dehydrating the calcium and magnesium ion precipitate by a sludge dehydration device 31 and then entering a sludge heating device 32, enabling the discharged liquid of a liquid discharge port 313 of the sludge dehydration device to flow back to a regulating tank 4 and then continuously enter the magnesium sulfate crystallization system 3, enabling the magnesium ion precipitate in the sludge heating device 32 to generate magnesium sulfate under the action of sulfuric acid and obtain a magnesium sulfate solution and a calcium sulfate precipitate, dehydrating the magnesium sulfate solution by a secondary dehydration device 33 and concentrating the magnesium sulfate solution by a second concentration device 34 to obtain a magnesium sulfate concentrated solution, and enabling the magnesium sulfate concentrated solution to obtain magnesium sulfate crystals under the action of the; the calcium sulfate is discharged from a dry sludge discharge port 334 of the secondary dehydration device, and the mother liquor discharged from a mother liquor outlet 353 of the second crystallization device flows back to the sludge inlet 322 of the heating device.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The utility model provides a system for desulfurization waste water draws magnesium sulfate and sodium chloride which characterized in that: comprises a pretreatment device (1), a sodium chloride crystallization system (2) and a magnesium sulfate crystallization system (3) which are respectively connected with the pretreatment device (1);
the pretreatment device (1) comprises a pretreatment device tank body (11), a pretreatment device water inlet (12) and a pretreatment device dosing port (13) which are arranged on the pretreatment device tank body (11), a pretreatment device supernatant outlet (14) which is arranged on the pretreatment device tank body (11) and is positioned on one side opposite to the pretreatment device water inlet (12), and a pretreatment device sludge outlet (15) which is arranged at the bottom of the pretreatment device tank body (11), wherein the pretreatment device dosing port (13) is used for dosing a medicament which enables calcium and magnesium ions in incoming water to form precipitate, and the pretreatment device tank body (11) is used for realizing coagulating sedimentation;
the sodium chloride crystallization system (2) comprises a filtering device (21), a nano-filtration salt separation device (22), a concentration device (23) and a crystallization device (24) which are connected in sequence;
the filtering device (21) comprises a filtering device body (211), a filtering device water inlet pipe (212) arranged at one end of the filtering device body (211), a filtering device water outlet (213) arranged on the filtering device body (211) and opposite to the filtering device water inlet pipe (212), and a filtering device dosing component (214) arranged on the filtering device water inlet pipe (212);
the nanofiltration salt separation device (22) comprises a nanofiltration salt separation device body (221), a nanofiltration salt separation device water inlet (222) arranged at one end of the nanofiltration salt separation device body (221), a nanofiltration salt separation device water inlet (223) arranged at the other side of the nanofiltration salt separation device body (221) and a nanofiltration salt separation device water outlet (224);
the concentration device (23) comprises a concentration device body (231), a concentration device water inlet (232) arranged on one side of the concentration device body (231), a concentration device water inlet (233) and a concentration device water outlet (234) arranged on the other side of the concentration device body (231);
the crystallization device (24) comprises a crystallization device body (241), and a crystallization device liquid inlet (242), a crystallization device mother liquid outlet (243) and a crystallization device discharge outlet (244) which are arranged on the crystallization device body (241);
the supernatant outlet (14) of the pretreatment device is connected with the water inlet pipe (212) of the filtration device, the water outlet (213) of the filtration device is connected with the water inlet (222) of the nano-filtration salt separation device, and the water outlet (224) of the nano-filtration salt separation device is connected with the water inlet (232) of the concentration device; the concentration device water inlet (233) is connected with the crystallization device liquid inlet (242); the filtering device dosing part (214) is used for dosing a second medicament:
the filtering device (21) precipitates calcium ions remained in the supernatant by adding a second medicament and filters the precipitates to obtain a filtrate, and the nano-filtration salt separating device (22) is used for separating monovalent ions and divalent ions in the filtrate and obtaining sodium chloride water; the concentration device (23) is used for concentrating the sodium chloride produced water to obtain a sodium chloride concentrated solution; the crystallizing device (24) is used for obtaining sodium chloride crystals from the sodium chloride concentrated solution, and a discharge port (244) of the crystallizing device is used for discharging sodium chloride crystals;
the magnesium sulfate crystallization system (3) comprises a sludge dehydration device (31), a heating device (32), a secondary dehydration device (33), a second concentration device (34) and a second crystallization device (35) which are connected in sequence;
the sludge dewatering device (31) comprises a sludge dewatering device body (311), a sludge dewatering device sludge inlet (312) arranged on one side of the sludge dewatering device body (311), a sludge dewatering device liquid outlet (313) arranged on the other side of the sludge dewatering device body (311) and a sludge dewatering device sludge outlet (314);
the heating device (32) comprises a heating device body (321), a heating device mud inlet (322) and a heating device medicine feeding part (323) which are arranged on the heating device body (321), and a heating device liquid outlet (324) which is arranged on the heating device body (321) and is positioned on the opposite side of the heating device mud inlet (322);
the secondary dehydration device (33) comprises a secondary dehydration device body (331), a secondary dehydration device water inlet (332) arranged on one side of the secondary dehydration device body (331), a secondary dehydration device liquid outlet (333) arranged on the other side of the secondary dehydration device body (331) and a secondary dehydration device dry mud discharge outlet (334);
the second concentration device (34) comprises a second concentration device body (341), a second concentration device water inlet (342) arranged at one side of the second concentration device body (341), and a second concentration device water inlet (343) arranged at the opposite side of the second concentration device body (341) to the second concentration device water inlet (342);
the second crystallization device (35) comprises a second crystallization device body (351), and a second crystallization device liquid inlet (352), a second crystallization device mother liquid outlet (353) and a second crystallization device discharge outlet (354) which are arranged on the second crystallization device body (351);
the sludge inlet (312) of the sludge dewatering device is connected with the sludge outlet (15) of the pretreatment device, the sludge inlet (322) of the heating device is connected with the sludge outlet (314) of the sludge dewatering device, the liquid outlet (324) of the heating device is connected with the water inlet (332) of the secondary dewatering device, the liquid outlet (333) of the secondary dewatering device is connected with the water inlet (342) of the second concentration device, and the water outlet (343) of the second concentration device is connected with the liquid inlet (352) of the second crystallization device; the heating device dosing part (323) is used for dosing a third medicament;
the sludge dewatering device (31) is used for dewatering the sludge discharged by the pretreatment device (1), and the warming device (32) is used for controlling the temperature and the pH value of the sludge and precipitating the magnesium ions under the action of the third agent to generate magnesium sulfate and obtain a magnesium sulfate solution; the secondary dehydration device (33) is used for removing calcium sulfate precipitate in the magnesium sulfate solution and discharging the calcium sulfate precipitate from a dry mud discharge port (334) of the secondary dehydration device; the second concentration device (34) is used for obtaining magnesium sulfate concentrated solution; the second crystallizing device (35) is used for obtaining magnesium sulfate crystals from the magnesium sulfate concentrated solution; the second crystallizing device discharge port (354) is used for discharging magnesium sulfate crystals.
2. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 1, is characterized in that: a regulating reservoir (4) is further arranged at the water inlet end of the pretreatment device (1), the regulating reservoir (4) comprises a regulating reservoir body (41), a regulating reservoir water inlet pipe (42) arranged on the regulating reservoir body (41), and a regulating reservoir water outlet (43) arranged on the regulating reservoir body (41) and positioned on one side opposite to the regulating reservoir water inlet pipe (42);
the adjusting tank water inlet pipe (42) is connected with the incoming water of the desulfurization wastewater, the adjusting tank water outlet (43) is connected with the pretreatment device water inlet (12), and the desulfurization wastewater enters the pretreatment device (1) after passing through the adjusting tank (4);
and a concentrated water port (223) of the nanofiltration salt separation device is connected with a regulating tank water inlet pipe (42).
3. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 2, is characterized in that: and the liquid outlet (313) of the sludge dewatering device is connected with the water inlet pipe (42) of the adjusting tank.
4. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 2, is characterized in that: and the mother liquor outlet (353) of the second crystallization device is connected with the sludge inlet (322) of the heating device.
5. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 1, is characterized in that: the agent added into the pretreatment device dosing port (13) is calcium hydroxide; the sediment discharged from the sludge discharge port (15) is magnesium hydroxide and calcium sulfate; the second medicament added by the medicament adding part (214) of the filtering device is sodium carbonate, so that calcium ions remained in the supernatant generate calcium carbonate precipitates and are filtered to be removed; the third medicament added by the heating device medicament adding part (323) is sulfuric acid.
6. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 1, is characterized in that: the tank body (11) is a high-density sedimentation tank or a mechanical accelerated clarification tank, the filtering device (21) is a tubular membrane filtering device, the tubular membrane filtering device adopts a tubular ultrafiltration membrane or a tubular microfiltration membrane, and the membrane pores are 0.05-0.2 um;
the concentration device (23) is a high pressure membrane concentration device using a high pressure roll membrane or a DTRO disc tube reverse osmosis membrane;
the crystallization device (24) is an MVR mechanical vapor recompression device;
the sludge dewatering device (31) is a centrifugal dewatering machine;
the secondary dewatering device (33) is a plate-and-frame filter press;
the second concentration device (34) is an evaporative concentration device;
the second crystallization device (35) is a freezing crystallization device.
7. A method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater is characterized by comprising the following steps: the method comprises the following steps:
s1, after desulfurization wastewater enters a pretreatment device (1), adding a medicament from a medicament adding port (13) of the pretreatment device to obtain calcium and magnesium ion precipitate and supernatant;
s2, enabling the supernate to enter a sodium chloride crystallization system (2) through a supernate outlet (14) of a pretreatment device, removing residual calcium ions from the supernate under the action of a second medicament added into a water inlet pipe (214) of a filtering device, filtering the supernate through the filtering device (2) to obtain a filtrate, enabling the filtrate to enter a nano-filtration salt separation device (22) to separate monovalent ions and divalent ions to obtain sodium chloride produced water, concentrating the sodium chloride produced water through a concentrating device (23) to obtain a sodium chloride concentrated solution, and enabling the sodium chloride concentrated solution to obtain sodium chloride crystals under the action of a crystallizing device (24);
s3, enabling a sludge discharge port (15) of the pretreatment device for calcium and magnesium ion precipitation to enter a magnesium sulfate crystallization system (3), dehydrating through a sludge dehydration device (31), enabling the sludge to enter a sludge heating device (32), enabling the magnesium ion precipitation in the sludge heating device (32) to generate magnesium sulfate under the action of a third agent to obtain a magnesium sulfate solution and a calcium sulfate precipitation, dehydrating through a secondary dehydration device (33) and concentrating through a second concentration device (34) to obtain a magnesium sulfate concentrated solution, and enabling the magnesium sulfate concentrated solution to obtain magnesium sulfate crystals under the action of a second crystallization device (35); the calcium sulfate sediment is discharged through a dry mud discharge port (334) of the secondary dewatering device.
8. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 7, wherein:
in the step S1, the desulfurization wastewater passes through a regulating tank (4) before entering the pretreatment device (1);
and in the step S2, the concentrated water of the nanofiltration salt separation device (22) flows back to the regulating tank (4) for regulating and homogenizing, and then continuously enters the sodium chloride crystallization system (2) and the magnesium sulfate crystallization system (3).
9. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as recited in claim 8, wherein: in the step S3, the discharged liquid of the liquid discharging port (313) of the sludge dewatering device flows back to the adjusting tank (4) for adjusting and homogenizing, and then continuously enters the sodium chloride crystallization system (2) and the magnesium sulfate crystallization system (3); and in the step S3, the mother liquor discharged from the mother liquor outlet (353) of the second crystallizing device flows back to the sludge inlet (322) of the heating device.
10. The system for extracting magnesium sulfate and sodium chloride from desulfurization wastewater as claimed in claim 7, wherein: in step S1, the agent is calcium hydroxide; the magnesium ion precipitate is magnesium hydroxide, and meanwhile, calcium sulfate precipitate is obtained; in step S2, the second agent is sodium carbonate, so that calcium ions remaining in the supernatant are precipitated into calcium carbonate and filtered out; the third agent is sulfuric acid in step S3, and magnesium hydroxide is precipitated to form magnesium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010781119.2A CN112441601A (en) | 2020-08-06 | 2020-08-06 | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010781119.2A CN112441601A (en) | 2020-08-06 | 2020-08-06 | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112441601A true CN112441601A (en) | 2021-03-05 |
Family
ID=74733486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010781119.2A Pending CN112441601A (en) | 2020-08-06 | 2020-08-06 | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112441601A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159753A (en) * | 2022-05-26 | 2022-10-11 | 江苏京源环保股份有限公司 | Zero discharge system and treatment method for magnesium desulfurization wastewater |
| CN115490355A (en) * | 2022-08-22 | 2022-12-20 | 安徽普朗膜技术有限公司 | Coal fired power plant desulfurization effluent treatment plant |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060196836A1 (en) * | 2002-11-05 | 2006-09-07 | Aharon Arakel | Process and apparatus for the treatment of saline water |
| CN101016175A (en) * | 2006-02-12 | 2007-08-15 | 山东滨化集团有限责任公司 | Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution |
| CN101724748A (en) * | 2008-10-07 | 2010-06-09 | 中国恩菲工程技术有限公司 | Method for leaching magnesium-containing ores |
| CN101760641A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Technology for recovering magnesium from magnesium sulfate solution |
| CN103553138A (en) * | 2013-11-01 | 2014-02-05 | 王文领 | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water |
| WO2017133514A1 (en) * | 2016-02-05 | 2017-08-10 | 大唐环境产业集团股份有限公司 | Treatment apparatus and method for softening desulfurization wastewater |
| CN109133440A (en) * | 2017-06-28 | 2019-01-04 | 北京朗新明环保科技有限公司 | A kind of desulfurization wastewater zero-discharge treatment system and technique |
| CN109928560A (en) * | 2017-12-18 | 2019-06-25 | 国家电投集团远达环保工程有限公司重庆科技分公司 | A kind of zero emission treatment of desulfured waste water and processing unit |
| CN110386710A (en) * | 2019-07-19 | 2019-10-29 | 北京朗新明环保科技有限公司南京分公司 | A method of epsom salt is produced using heat-engine plant desulfurized waste water |
| CN214570785U (en) * | 2020-08-06 | 2021-11-02 | 国能朗新明环保科技有限公司 | System for extracting magnesium sulfate and sodium chloride from desulfurization wastewater |
-
2020
- 2020-08-06 CN CN202010781119.2A patent/CN112441601A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060196836A1 (en) * | 2002-11-05 | 2006-09-07 | Aharon Arakel | Process and apparatus for the treatment of saline water |
| CN101016175A (en) * | 2006-02-12 | 2007-08-15 | 山东滨化集团有限责任公司 | Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution |
| CN101724748A (en) * | 2008-10-07 | 2010-06-09 | 中国恩菲工程技术有限公司 | Method for leaching magnesium-containing ores |
| CN101760641A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Technology for recovering magnesium from magnesium sulfate solution |
| CN103553138A (en) * | 2013-11-01 | 2014-02-05 | 王文领 | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water |
| WO2017133514A1 (en) * | 2016-02-05 | 2017-08-10 | 大唐环境产业集团股份有限公司 | Treatment apparatus and method for softening desulfurization wastewater |
| CN109133440A (en) * | 2017-06-28 | 2019-01-04 | 北京朗新明环保科技有限公司 | A kind of desulfurization wastewater zero-discharge treatment system and technique |
| CN109928560A (en) * | 2017-12-18 | 2019-06-25 | 国家电投集团远达环保工程有限公司重庆科技分公司 | A kind of zero emission treatment of desulfured waste water and processing unit |
| CN110386710A (en) * | 2019-07-19 | 2019-10-29 | 北京朗新明环保科技有限公司南京分公司 | A method of epsom salt is produced using heat-engine plant desulfurized waste water |
| CN214570785U (en) * | 2020-08-06 | 2021-11-02 | 国能朗新明环保科技有限公司 | System for extracting magnesium sulfate and sodium chloride from desulfurization wastewater |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159753A (en) * | 2022-05-26 | 2022-10-11 | 江苏京源环保股份有限公司 | Zero discharge system and treatment method for magnesium desulfurization wastewater |
| CN115159753B (en) * | 2022-05-26 | 2023-08-18 | 江苏京源环保股份有限公司 | Zero discharge system for magnesium desulfurization wastewater and treatment method thereof |
| CN115490355A (en) * | 2022-08-22 | 2022-12-20 | 安徽普朗膜技术有限公司 | Coal fired power plant desulfurization effluent treatment plant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108249646B (en) | Power plant desulfurization wastewater zero-emission treatment process and device capable of recycling resources | |
| CN106830479A (en) | Using flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system and method | |
| CN104843927A (en) | Desulfurization waste water zero discharging process and system | |
| CN103449653A (en) | Combined treatment method for sodium chloride-containing wastewater generated in dressing and smelting of rare earth | |
| CN108623063A (en) | A kind of processing method and processing system of desulfurization wastewater | |
| CN111362283B (en) | Viscose wastewater recycling treatment method | |
| CN113800690A (en) | Power plant desulfurization wastewater zero-discharge treatment process and system based on electrodialysis technology | |
| CN102030441A (en) | Method for treating wastewater in production of sebacic acid | |
| CN111718048A (en) | Wet desulphurization waste water and salt separation zero-emission system and salt separation zero-emission method | |
| CN208120896U (en) | Can resource recycling power plant desulfurization wastewater zero discharge treatment device | |
| CN106966535A (en) | Strong brine zero-emission film is concentrated and sub-prime crystallization processes and equipment | |
| CN104591459A (en) | Acid and alkali resource recovery process technology from sodium saponification waste water | |
| CN110937728A (en) | Desulfurization wastewater treatment method and system | |
| CN104909494A (en) | Process for impurity removal and purification of industrial high-concentration brine and special equipment of process | |
| CN111170544A (en) | Zero discharge system and method for pretreatment wastewater of active coke desulfurization and denitrification and salt preparation from rich gas | |
| CN112441601A (en) | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater | |
| CN111170516A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN111170519A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN106492615B (en) | Desulfurization method and desulfurization system for coal-fired flue gas | |
| CN105481160B (en) | Method and device for preparing industrial salt by strong brine with zero discharge | |
| CN107055886B (en) | A kind of depth graded divides salt technique | |
| CN214570785U (en) | System for extracting magnesium sulfate and sodium chloride from desulfurization wastewater | |
| CN205933496U (en) | Desulfurization waste water zero release processing apparatus based on electrodialysis | |
| CN109607582B (en) | Method and system for recovering magnesium salt from desulfurization wastewater | |
| CN209923115U (en) | Salt recovery system and processing system for salt-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100039 501, 502, 5th floor, building 1, yard 16, West Fourth Ring Middle Road, Haidian District, Beijing Applicant after: Guoneng Lang Xinming Environmental Protection Technology Co.,Ltd. Address before: 100039 501, 502, 5th floor, building 1, yard 16, West Fourth Ring Middle Road, Haidian District, Beijing Applicant before: BEIJING LUCENCY ENVIRO-TECH Co.,Ltd. |
|
| CB02 | Change of applicant information |