CN114149113A - Resourceful treatment device and method for high-salinity wastewater - Google Patents
Resourceful treatment device and method for high-salinity wastewater Download PDFInfo
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- CN114149113A CN114149113A CN202010929041.4A CN202010929041A CN114149113A CN 114149113 A CN114149113 A CN 114149113A CN 202010929041 A CN202010929041 A CN 202010929041A CN 114149113 A CN114149113 A CN 114149113A
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- 238000000034 method Methods 0.000 title claims abstract description 32
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- 238000001223 reverse osmosis Methods 0.000 claims abstract description 111
- 238000001914 filtration Methods 0.000 claims abstract description 70
- 238000002425 crystallisation Methods 0.000 claims abstract description 59
- 230000008025 crystallization Effects 0.000 claims abstract description 59
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 49
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- 230000003647 oxidation Effects 0.000 claims abstract description 40
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 230000004907 flux Effects 0.000 claims description 32
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 19
- 238000010517 secondary reaction Methods 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 239000003245 coal Substances 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
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- 239000000463 material Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 159000000007 calcium salts Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000008394 flocculating agent Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 description 24
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- 239000011737 fluorine Substances 0.000 description 18
- 229910052731 fluorine Inorganic materials 0.000 description 18
- 238000005374 membrane filtration Methods 0.000 description 14
- 238000004064 recycling Methods 0.000 description 12
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000006115 defluorination reaction Methods 0.000 description 3
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/60—Silicon compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/19—SO4-S
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a resource treatment device for high-salinity wastewater, which comprises: the device comprises a hard removal filtering unit, an ozone catalytic oxidation unit, an ultrafiltration unit, a high-pressure reverse osmosis unit, a primary nanofiltration unit, a secondary nanofiltration unit, a roll type reverse osmosis unit, a first evaporative crystallization unit and a second evaporative crystallization unit. Compared with the prior art, the device and the process have the advantages of good effluent quality, high quality of recycled salt and good technical economy.
Description
Technical Field
The invention relates to the technical field of high-salinity wastewater treatment, in particular to a recycling treatment device and a treatment method for high-salinity wastewater.
Background
The Chinese energy condition belongs to the type of rich coal and lean oil, and the coal chemical technology occupies a very important position in the regeneration and consumption of energy. The coal chemical industry is a process of converting coal into gas, liquid and solid raw materials by using coal as a raw material through chemical processing, and mainly comprises the steps of coal vaporization, liquefaction, dry distillation, tar processing and the like. The application development of the coal chemical industry inevitably generates a large amount of waste water, the waste water mainly contains a large amount of organic matters and inorganic salts, the water quality is complex, and the effective treatment of the waste water is the key of the sustainable development of coal chemical industry enterprises.
Part of enterprises generally adopt a combined process of 'pretreatment-membrane concentration-evaporative crystallization' to treat high-salinity wastewater, and NaCl and Na are finally produced2SO4The mixed salt is treated, but the mixed salt is used as dangerous waste and has no good means for realizing reasonable removal. Therefore, in order to truly realize the aim of 'salt separation and zero discharge' of high-salinity wastewater, the method for separating sodium chloride from sodium sulfate by using resources is the key for truly realizing the improvement of the salt separation efficiency of evaporative crystallization and the recycling of salts.
In addition, fluorine element in the raw coal exists in the wastewater in an ionic state, and high concentration fluorine ions are seriously corroded to an evaporator in the concentration and evaporation process, so that the fluorine element needs to be effectively removed before entering an evaporation crystallizer. At present, the wastewater defluorination is usually carried out by a calcium-adding defluorination method, and an effective technical means for the synergy of defluorination and salt separation of the whole process is still lacked.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a recycling apparatus for high-salinity wastewater, which can effectively treat high-salinity wastewater and obtain valuable products such as sodium sulfate, sodium chloride, and produced water meeting the recycling standards of recycled water, etc. by using a combination of a hardness-removing filtration unit, an ozone catalytic oxidation unit, an ultrafiltration unit, a high-pressure reverse osmosis unit, a primary nanofiltration unit, a secondary nanofiltration unit, a roll-type reverse osmosis unit, a first evaporative crystallization unit, and a second evaporative crystallization unit.
The second purpose of the invention is to provide a resource treatment method of high-salinity wastewater corresponding to the first purpose.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a resourceful treatment device for high-salinity wastewater comprises: the device comprises a hard removal filtering unit, an ozone catalytic oxidation unit, an ultrafiltration unit, a high-pressure reverse osmosis unit, a primary nanofiltration unit, a secondary nanofiltration unit, a roll type reverse osmosis unit, a first evaporative crystallization unit and a second evaporative crystallization unit; the device comprises a hard-removing filtering unit, an ozone catalytic oxidation unit, a first-stage nanofiltration unit, a second-stage nanofiltration unit and a third-stage nanofiltration unit, wherein a water outlet of the hard-removing filtering unit is connected with a water inlet of the ozone catalytic oxidation unit, a water outlet of the ozone catalytic oxidation unit is connected with a water inlet of the ultrafiltration unit, a water outlet of the ultrafiltration unit is connected with a water inlet of the high-pressure reverse osmosis unit, a concentrated water outlet of the first-stage nanofiltration unit is connected with a water inlet of the first-stage nanofiltration unit, a concentrated water outlet of the first-stage nanofiltration unit is connected with a water inlet of the second-stage nanofiltration unit, a concentrated water outlet of the second-stage nanofiltration unit is connected with a water inlet of the second-stage nanofiltration unit, and a concentrated water outlet of the second-stage nanofiltration unit is connected with a water inlet of the second-stage reverse osmosis unit.
In some preferred embodiments of the present invention, the concentrated water outlet of the secondary nanofiltration unit is connected to the water inlet of the primary nanofiltration unit.
In some preferred embodiments of the present invention, the hardness-removing filtering unit comprises a primary reaction tank, a secondary reaction tank, a primary sedimentation tank and a filtering device, wherein a partition is arranged between the primary reaction tank and the secondary reaction tank, a water outlet of the secondary reaction tank is connected with a water inlet of the primary sedimentation tank, and a water outlet of the primary sedimentation tank is connected with a water inlet of the filtering device.
According to the invention, a partition plate is arranged between the primary reaction tank and the secondary reaction tank, so that the effluent in the primary reaction tank can enter the secondary reaction tank in an overflow mode.
In some preferred embodiments of the present invention, the primary reaction tank is provided with a soluble calcium salt dosing device and a magnesium agent dosing device, and the secondary reaction tank is provided with a sodium carbonate dosing device, a flocculant dosing device and a sodium hydroxide dosing device.
According to the invention, the hard removal filtering unit can synergistically remove calcium ions, magnesium ions, silicon ions and fluorine ions in the high-salinity wastewater.
In some preferred embodiments of the present invention, the first-stage nanofiltration unit employs a disk-and-tube nanofiltration membrane module.
According to some specific embodiments of the present invention, the membrane module of the first-stage nanofiltration unit is in the form of a plurality of disc-type membrane sheets connected in series on a central tube to form a disc-type membrane column.
In some preferred embodiments of the present invention, the secondary nanofiltration unit employs a roll-to-roll nanofiltration membrane module.
According to some specific embodiments of the present invention, the ozone catalytic oxidation unit comprises an ozone generator, an ozone reaction tank filled with a catalyst, and an effluent standing tank.
According to the invention, the ozone catalytic oxidation unit can remove organic matters in the high-salinity wastewater.
According to some specific embodiments of the present invention, the ultrafiltration unit employs pressure-type ultrafiltration, and the components are selected from external pressure-type hollow fiber ultrafiltration membrane components.
According to the invention, the ultrafiltration unit can remove suspended matters in the high-salinity wastewater and reduce the turbidity of the high-salinity wastewater.
According to some embodiments of the invention, the high pressure reverse osmosis unit uses a wound reverse osmosis membrane module.
According to the invention, the high pressure reverse osmosis unit is capable of concentrating the incoming water to increase the concentration of sodium sulfate and sodium chloride in the effluent.
According to some specific embodiments of the invention, the rolled reverse osmosis unit employs a rolled reverse osmosis membrane module.
According to the invention, the roll-up reverse osmosis unit is capable of concentrating incoming water to increase the concentration of sodium chloride in the effluent.
According to some specific embodiments of the invention, the first evaporative crystallization unit is a four-effect evaporative crystallizer.
According to some specific embodiments of the invention, the second evaporative crystallization unit is a four-effect evaporative crystallizer.
According to some specific embodiments of the present invention, the first and second evaporative crystallization units may employ waste steam heating as a heat source.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a method for treating high-salinity wastewater in coal chemical industry by using the recycling treatment device comprises the following steps:
s1, introducing high-salinity wastewater into the hardness-removing filtering unit to form a filtering concentrated phase and filtering produced water;
s2, introducing the filtered produced water into the ozone catalytic oxidation unit to form ozone catalytic oxidation effluent;
s3, introducing the effluent of the catalytic oxidation of ozone into the ultrafiltration unit to form ultrafiltration water;
s4, introducing the ultrafiltration produced water into the high-pressure reverse osmosis unit to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water;
s5, introducing the high-pressure reverse osmosis concentrated water into the primary nanofiltration unit to form primary nanofiltration concentrated water and primary nanofiltration produced water;
s6, introducing the primary nanofiltration concentrated water into the first evaporative crystallization unit to obtain sodium sulfate solid and first evaporative crystallization water;
s7, introducing the primary nanofiltration water product into the secondary nanofiltration unit to obtain secondary nanofiltration concentrated water and secondary nanofiltration water product;
s8, introducing the secondary nanofiltration produced water into the roll type reverse osmosis unit to obtain roll type reverse osmosis produced water and roll type reverse osmosis concentrated water, and preferably introducing the secondary nanofiltration concentrated water into the primary nanofiltration unit;
and S9, introducing the rolled reverse osmosis concentrated water into the second evaporative crystallization unit to obtain sodium chloride solid and second evaporative crystallization water.
According to the invention, the high-pressure reverse osmosis water production, the roll type reverse osmosis water production, the first evaporative crystallization water production and the second evaporative crystallization water production have the conductivities of less than 1200 mu S/cm, the Chemical Oxygen Demand (COD) of less than 60mg/L and Cl-The concentration is less than 200mg/L, and the water replenishing and recycling standard of circulating water is met.
According to the invention, the high-pressure reverse osmosis produced water, the roll type reverse osmosis produced water, the first evaporative crystallization produced water and the second evaporative crystallization produced water can be independently used or mixed in any mode and then recycled for production process or circulating water replenishing.
In some preferred embodiments of the present invention, step S1 includes:
a) introducing the high-salinity wastewater into the primary reaction tank, and adding soluble calcium salt and a magnesium agent into the primary reaction tank;
b) overflowing the effluent of the primary reaction tank to the secondary reaction tank, adding sodium carbonate, a flocculating agent and sodium hydroxide into the primary reaction tank, preferably adding the sodium carbonate and the flocculating agent first, and then adding the sodium hydroxide;
c) the effluent of the secondary reaction tank enters the primary sedimentation tank;
d) and leading the effluent of the primary sedimentation tank to enter the filtering device, thereby forming the filtering concentrated phase and the filtering produced water.
According to the invention, the concentrated filtration phase can be treated in a centralized manner after being dewatered and solidified by sludge.
In some preferred embodiments of the invention, the soluble calcium salt is calcium chloride and/or calcium hydroxide.
In some preferred embodiments of the invention, the magnesium agent is selected from one or more of magnesium oxide, magnesium chloride and magnesium sulfate.
In some preferred embodiments of the invention, the flocculating agent is selected from polyaluminium chloride and/or polyferric sulphate.
In some preferred embodiments of the present invention, the soluble calcium salt is added in an amount of 0.8g to 1.5g per increased salt content of the wastewater.
In some preferred embodiments of the present invention, the magnesium agent is added in an amount of 0.8g to 2.0g per rise of the salt waste water.
In some preferred embodiments of the present invention, the sodium carbonate is added in an amount of 1.0g to 1.8g per liter of the saline wastewater.
In some preferred embodiments of the present invention, the flocculant is added in an amount of 0.1g to 0.3g per rise of the saline wastewater.
In some preferred embodiments of the present invention, the sodium hydroxide is added in an amount such that the pH of the high-salinity wastewater in the secondary reaction tank is 10.5 to 11.5.
According to the invention, the retention time of the high-salinity wastewater in the primary reaction tank is 15-30 min.
According to the invention, the retention time of the high-salinity wastewater in the secondary reaction tank is 15-30 min.
In some preferred embodiments of the present invention, the membrane material used in the filtration device is a polytetrafluoroethylene membrane, preferably a polytetrafluoroethylene membrane with a membrane pore size of 0.15 μm to 0.25 μm.
In some preferred embodiments of the present invention, the filtration pressure of the filtration device is 0.08MPa to 0.15MPa, and the membrane flux is 200L/m2·h～400L/m2·h。
In some preferred embodiments of the present invention, the water quality of the coal chemical industry high-salinity wastewater is characterized by: the pH value is 7.5-8.5; and/or the total soluble solid concentration is 10000 mg/L-20000 mg/L; and/or Cl-The concentration is 4000 mg/L-7000 mg/L; and/or SO4 2-The concentration is 2000 mg/L-4000 mg/L; and/or Mg2+The concentration is 30 mg/L-90 mg/L; and/or Ca2+The concentration is 50 mg/L-150 mg/L; and/or the concentration of dissolved silicon is 50 mg/L-150 mg/L; and/or F-The concentration is 50 mg/L-80 mg/L; and/or HCO3 -The concentration is 300 mg/L-500 mg/L; and/or chemical oxygen demand of 80mg/L E120mg/L。
In some preferred embodiments of the present invention, in step S2, the ozone catalytic oxidation unit employs an activated carbon-based catalyst.
In some preferred embodiments of the present invention, in step S2, the operating conditions of the ozone catalytic oxidation unit include: the pH value of the inlet water is 7.0-9.0, preferably 7.5-8.5, and/or the inlet water temperature is 5-35 ℃, preferably 15-30 ℃, and/or the residence time is 0.1-5 h, preferably 1-2 h, and/or the ozone concentration is 100-250 mg/L, preferably 150-200 mg/L.
In some preferred embodiments of the present invention, in step S3, the operating conditions of the ultrafiltration unit include: the filtration pressure is 0.05MPa to 0.15MPa, preferably 0.08MPa to 0.12 MPa.
In some preferred embodiments of the present invention, in step S4, the operating conditions of the high pressure reverse osmosis unit include: the operation pressure is 1MPa to 10MPa, preferably 4MPa to 6MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 5L/m2·h～20L/m2H, preferably 10L/m2·h～15L/m2H and/or a recovery rate of 40% to 70%, preferably 50% to 60%.
In some preferred embodiments of the present invention, in step S5, the operating conditions of the primary nanofiltration unit include: the operation pressure is 1MPa to 5MPa, preferably 3MPa to 4MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 5L/m2·h～20L/m2H, preferably 8L/m2·h～15L/m2H and/or a recovery rate of 65% to 80%, preferably 70% to 65%.
In some preferred embodiments of the present invention, in step S7, the operating conditions of the secondary nanofiltration unit include: the operation pressure is 1MPa to 5MPa, preferably 2MPa to 3MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 10L/m2·h～25L/m2H, preferably 13L/m2·h～20L/m2H and/or a recovery rate of 70% to 85%, preferably 75% to 80%.
According to the invention, the concentrated water outlet of the primary nanofiltration unit is provided with a partial reflux process, namely, the primary nanofiltration concentrated water returns to the primary nanofiltration water inlet and is mixed with the inlet water to be used as the primary nanofiltration inlet water, and the reflux ratio is 40-50%.
According to the present invention, the reflux ratio may be set to 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% and any value therebetween.
In some preferred embodiments of the invention, the mass ratio of the chloride ions to the sulfate ions in the water produced by the secondary nanofiltration is (50-70): 1, preferably (55-60): 1.
In some preferred embodiments of the invention, the mass ratio of sulfate ions to chloride ions in the first-stage nanofiltration concentrated water is (10-20): 1, preferably (15-18): 1.
In some preferred embodiments of the invention, in step S8, the operating conditions of the roll-to-roll reverse osmosis unit include: the operation pressure is 1MPa to 10MPa, preferably 3MPa to 5MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 10L/m2·h～25L/m2H, preferably 13L/m2·h～18L/m2H and/or a recovery rate of 40% to 70%, preferably 50% to 60%.
According to the invention, the concentration of calcium ions is less than 10mg/L, the concentration of magnesium ions is less than 10mg/L, the concentration of dissolved silicon is less than 20mg/L, and the concentration of fluorine ions is less than 20mg/L in the filtered water.
According to the invention, the COD of the water discharged by the catalytic oxidation of the ozone is 30 mg/L-60 mg/L.
According to some embodiments of the present invention, the evaporative crystallization operations in step S6 and step S7 are conventional operations in the art, and may be performed in any manner known in the art, which is not a focus of the present invention and is not described herein.
According to some embodiments of the present invention, the evaporative crystallization operations in step S6 and in step S9 may employ a low temperature heat source, such as waste heat steam.
According to some embodiments of the present invention, in step S6, the obtained sodium sulfate salt has a purity of 98% or more after separation and drying, which meets class ii first-class standard in GB/T6009-2014.
According to some embodiments of the present invention, in step S9, the obtained sodium chloride salt has a purity of 98% or more after separation and drying, and reaches the primary standard of refined industrial salt in GB/T5462-2015 Industrial salt standard.
According to the device and the method for recycling the high-salinity wastewater, disclosed by the invention, on the basis of effectively treating the high-salinity wastewater, the water resource recovery in the wastewater and the quality-divided crystallization and resource utilization of salts are realized, the problem of difficult treatment caused by a large amount of pollutants and high concentration of pollutants in the high-salinity wastewater is solved, and the near zero emission of the high-salinity wastewater is realized. The system produced water formed after being treated by the device and the method can be directly recycled for supplementing circulating water, so that the advanced treatment and recycling of wastewater are realized, and the high-purity sodium sulfate and sodium chloride obtained after being treated by the method can be recycled as renewable resources.
The substantial difference between the present invention and the prior art is: aiming at the technical defects of the prior art, the high-salinity wastewater is treated by adopting high-efficiency hardness removal filtration, ozone catalytic oxidation, ultrafiltration, high-pressure reverse osmosis, two-stage nanofiltration, roll type reverse osmosis and evaporative crystallization. Compared with the prior art, the process provided by the invention has the advantages of good effluent quality, high quality of recycled salts and good technical economy.
The beneficial effects are as follows:
1. the invention adopts the high-efficiency hardness removal filtering process to treat the pollutants such as hardness and the like in the high-salinity wastewater, can effectively remove the calcium, magnesium, silicon and fluorine pollutants and other suspended matters in the wastewater in one step by optimizing the dosing process and the dosing formula, and has the advantages of good treatment effect, excellent effluent quality, simple equipment, high automation degree, easy operation and maintenance, strong environment adaptability and small occupied area;
2. according to the invention, firstly, high-salt wastewater is further concentrated by adopting high-pressure reverse osmosis, and secondly, high-pressure reverse osmosis concentrated water is further subjected to quality separation treatment by adopting two-stage nanofiltration, so that the technical advantages of the high-pressure reverse osmosis concentrated water and the high-pressure reverse osmosis concentrated water are fully combined, the treatment scale of a nanofiltration unit is reduced, the operation cost is reduced, and the salt quality separation crystallization in the wastewater is realized;
3. the invention adopts the four-effect evaporation technology to treat the primary nanofiltration concentrated water and the roll type reverse osmosis concentrated water, fully utilizes the low-temperature heat source of a factory, and reduces the operation cost;
4. the method provided by the invention is adopted to carry out the quality-divided crystallization of the high-salinity wastewater, so that the problem of difficult treatment caused by a large amount of pollutants and high concentration of pollutants in the high-salinity wastewater is solved, the near zero emission of the high-salinity wastewater is realized, and the resource utilization of water resources and salts is realized.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
Example 1
The main water quality characteristics of the coal chemical industry high salt waste water that handles in this example are: pH 7.5, Total Dissolved Solids (TDS) concentration 10000mg/L, Cl-In a concentration of 4000mg/L, SO4 2-In a concentration of 2000Mg/L, Mg2+Has a concentration of 30mg/L, Ca2+Has a concentration of 50mg/L, a concentration of dissolved silicon of 50mg/L, F-Has a concentration of 50mg/L, HCO3 -The concentration of (A) was 300mg/L and the concentration of COD was 80 mg/L.
The process flow is shown in figure 1, and comprises the following specific steps:
step 1, treating the high-salinity wastewater in a high-efficiency hardness removal filtering unit. Firstly, adding calcium chloride and magnesium chloride into a first-stage reaction tank, wherein the adding concentration is 0.8g/L, the reaction time is 15min, overflowing effluent into a second-stage reaction tank, adding sodium carbonate and polyaluminium chloride, the adding concentration of the sodium carbonate is 1.0g/L, and the adding concentration of the polyaluminium chloride is 0.1 g/L; then adding sodium hydroxide, adjusting the pH value of the wastewater to 10.8, reacting for 15min, allowing the effluent to enter a primary sedimentation tank to generate hard calcium, hard magnesium, silicates, fluorides and complexes thereof and other various precipitates, and allowing the effluent of the primary sedimentation tank to enter a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.08MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.15 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 400L/m2H is about; the Suspended Substance (SS) of the effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is less than 10mg/L, the magnesium ion concentration is less than 10mg/L, the dissolved silicon concentration is less than 20mg/L, and the fluorine ion concentration is less than 20 mg/L;
step 2, the high-efficiency hardness removal filtration produced water enters an ozone catalytic oxidation unit for treatment, the ozone catalytic oxidation unit adopts an active carbon-based catalyst, and the operation conditions are as follows: the pH value of inlet water is 7.5, the inlet water temperature is 15 ℃, the retention time is 1h, and the ozone concentration is 150 mg/L.
Under the condition, COD of the effluent water of the ozone catalytic oxidation is about 30 mg/L;
step 3, the effluent of the catalytic oxidation of ozone enters an ultrafiltration unit for treatment, the ultrafiltration unit adopts pressure type ultrafiltration, an external pressure type hollow fiber ultrafiltration membrane component is adopted as the component, and the filtration pressure is 0.08 MPa;
under the condition, the turbidity of the ultrafiltration produced water is less than 0.1 NTU; the concentrated phase of ultrafiltration is treated by centralized transportation after sludge dehydration and solidification;
step 4, the ultrafiltration produced water enters a high-pressure reverse osmosis unit for treatment, the high-pressure reverse osmosis unit adopts a roll type reverse osmosis membrane component, and the operation conditions are as follows: the operation pressure is 4MPa, and the pH value of inlet water is 7.5;
under the condition, the membrane flux of the high-pressure reverse osmosis unit is 13-15L/m2H, the recovery rate of the high-pressure reverse osmosis unit is 60%, and the TDS of the high-pressure reverse osmosis concentrated water is about 25000 mg/L;
and step 5, the high-pressure reverse osmosis concentrated water enters a two-stage nanofiltration unit for treatment, a disc-tube nanofiltration membrane component is adopted in the first-stage nanofiltration in the two-stage nanofiltration unit, and in operation, 50% of the first-stage nanofiltration concentrated water returns to the first-stage nanofiltration water inlet and is mixed with inlet water to be used as first-stage nanofiltration inlet water. The operation conditions of the first-stage nanofiltration are as follows: the operation pressure is 3MPa, and the pH value of inlet water is 7.5; the second-stage nanofiltration adopts a roll-type nanofiltration membrane component, and the operating conditions of the second-stage nanofiltration are as follows: the operation pressure is 2MPa, and the pH value of inlet water is 7.5;
under the condition, the membrane flux of the primary nanofiltration is 13-15L/m2H, the recovery rate is 70-75%; the membrane flux of the secondary nanofiltration is 18-20L/m2H, the recovery rate is 75-80%; the mass ratio of chloride ions to sulfate ions in the water produced by the secondary nanofiltration is 55: 1; the mass ratio of sulfate ions to chloride ions in the first-stage nanofiltration concentrated water is 15: 1;
step 6, the water produced by the secondary nanofiltration enters a roll type reverse osmosis unit for treatment, a roll type reverse osmosis membrane component is adopted in roll type reverse osmosis, and the operation conditions are as follows: the operating pressure is 3MPa, and the pH value of inlet water is 7.5;
under the condition, the membrane flux of the roll type reverse osmosis unit is 16-18L/m2H, the recovery rate of the roll type reverse osmosis unit is 60%;
step 7, the primary nanofiltration concentrated water enters an evaporation crystallization unit for evaporation crystallization treatment to obtain sodium sulfate salts and evaporation crystallization water, and the obtained sodium sulfate salt is separated and dried to obtain sodium sulfate salt with purity of more than 98% and reaches class II first-class standard in GB/T6009-2014 Standard of Industrial anhydrous sodium sulfate;
and 8, allowing the roll-type reverse osmosis concentrated water to enter an evaporative crystallization unit for evaporative crystallization treatment to obtain sodium chloride salts and evaporative crystallization produced water, and separating and drying the obtained sodium chloride salts to obtain sodium chloride salts with purity of over 98 percent, wherein the sodium chloride salts reach the primary standard of refined industrial salt in GB/T5462-2015 Industrial salt standards.
Wherein, the water conductivity of the high-pressure reverse osmosis produced water, the spiral reverse osmosis produced water and the evaporative crystallization produced water after being mixed is less than 1200 mu S/cm, the COD is less than 60mg/L, and the Cl is-Less than 200mg/L, and meets the water replenishing and recycling requirements of recycled circulating water.
Example 2
The main water quality characteristics of the coal chemical industry high salt waste water that handles in this example are: pH 8, concentration of Total Dissolved Solids (TDS) 15000mg/L,Cl-has a concentration of 5500mg/L, SO4 2-In a concentration of 3000Mg/L, Mg2+Has a concentration of 60mg/L, Ca2+Has a concentration of 100mg/L, a concentration of dissolved silicon of 100mg/L, F-Has a concentration of 60mg/L, HCO3 -The concentration of (A) was 400mg/L and the concentration of COD was 100 mg/L.
The method comprises the following specific steps:
step 1, treating the high-salinity wastewater in a high-efficiency hardness removal filtering unit. Firstly, adding calcium chloride and magnesium chloride into a primary reaction tank, wherein the adding concentrations are 1.1g/L and 1.5g/L respectively, the reaction time is 20min, overflowing effluent into a secondary reaction tank, adding sodium carbonate and polyaluminium chloride, the adding concentration of the sodium carbonate is 1.5g/L, and the adding concentration of the polyaluminium chloride is 0.2 g/L; then adding sodium hydroxide, adjusting the pH value of the wastewater to 11.2, reacting for 20min, allowing the effluent to enter a primary sedimentation tank to generate hard calcium, hard magnesium, silicates, fluorides and complexes thereof and other various precipitates, and allowing the effluent of the primary sedimentation tank to enter a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.12MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.2 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 300L/m2H is about; the SS of effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is less than 10mg/L, the magnesium ion concentration is less than 10mg/L, the concentration of dissolved silicon is less than 20mg/L, and the concentration of fluorine ions is less than 20 mg/L;
step 2, the high-efficiency hardness removal filtration produced water enters an ozone catalytic oxidation unit for treatment, the ozone catalytic oxidation unit adopts an active carbon-based catalyst, and the operation conditions are as follows: the pH value of inlet water is 8, the inlet water temperature is 20 ℃, the retention time is 1.5h, and the ozone concentration is 170 mg/L.
Under the condition, COD of the effluent of the ozone catalytic oxidation is about 40 mg/L;
step 3, the effluent of the catalytic oxidation of ozone enters an ultrafiltration unit for treatment, the ultrafiltration unit adopts pressure type ultrafiltration, an external pressure type hollow fiber ultrafiltration membrane component is adopted as the component, and the filtration pressure is 0.1 MPa;
under the condition, the turbidity of the ultrafiltration produced water is less than 0.1 NTU; the concentrated phase of ultrafiltration is treated by centralized transportation after sludge dehydration and solidification;
step 4, the ultrafiltration produced water enters a high-pressure reverse osmosis unit for treatment, the high-pressure reverse osmosis unit adopts a roll type reverse osmosis membrane component, and the operation conditions are as follows: the operation pressure is 5MPa, and the pH value of inlet water is 8;
under the condition, the membrane flux of the high-pressure reverse osmosis unit is 12-14L/m2H, the recovery rate of the high-pressure reverse osmosis unit is 55%, and the TDS of the high-pressure reverse osmosis concentrated water is about 33000 mg/L;
and step 5, the high-pressure reverse osmosis concentrated water enters a two-stage nanofiltration unit for treatment, a disc-tube nanofiltration membrane component is adopted in the first-stage nanofiltration in the two-stage nanofiltration unit, and 55% of the first-stage nanofiltration concentrated water returns to the first-stage nanofiltration water inlet and is mixed with inlet water to serve as first-stage nanofiltration inlet water during operation. The operation conditions of the first-stage nanofiltration are as follows: the operation pressure is 3.5MPa, and the pH value of inlet water is 8; the second-stage nanofiltration adopts a roll-type nanofiltration membrane component, and the operating conditions of the second-stage nanofiltration are as follows: the operation pressure is 2.5MPa, and the pH value of inlet water is 8;
under the condition, the membrane flux of the primary nanofiltration is 11-13L/m2H, the recovery rate is 72%, and the membrane flux of the secondary nanofiltration is 16-18L/m2H, recovery of 78%; the mass ratio of chloride ions to sulfate ions in the water produced by the secondary nanofiltration is 57: 1; the mass ratio of sulfate ions to chloride ions in the first-stage nanofiltration concentrated water is 17: 1;
step 6, the water produced by the secondary nanofiltration enters a roll type reverse osmosis unit for treatment, a roll type reverse osmosis membrane component is adopted in roll type reverse osmosis, and the operation conditions are as follows: the operation pressure is 4MPa, and the pH value of inlet water is 8;
under the condition, the membrane flux of the roll type reverse osmosis unit is 15-17L/m2H, the recovery rate of the roll-type reverse osmosis unit is 56%;
step 7, the primary nanofiltration concentrated water enters an evaporation crystallization unit for evaporation crystallization treatment to obtain sodium sulfate salts and evaporation crystallization water, and the obtained sodium sulfate salt is separated and dried to obtain sodium sulfate salt with purity of more than 98% and reaches class II first-class standard in GB/T6009-2014 Standard of Industrial anhydrous sodium sulfate;
and 8, allowing the roll-type reverse osmosis concentrated water to enter an evaporative crystallization unit for evaporative crystallization treatment to obtain sodium chloride salts and evaporative crystallization produced water, and separating and drying the obtained sodium chloride salts to obtain sodium chloride salts with purity of over 98 percent, wherein the sodium chloride salts reach the primary standard of refined industrial salt in GB/T5462-2015 Industrial salt standards.
Wherein, the water conductivity of the high-pressure reverse osmosis produced water, the spiral reverse osmosis produced water and the evaporative crystallization produced water after being mixed is less than 1200 mu S/cm, the COD is less than 60mg/L, and the Cl is-Less than 200mg/L, and meets the water replenishing and recycling requirements of recycled circulating water.
Example 3
The main water quality characteristics of the coal chemical industry high salt waste water that handles in this example are: pH 8.5, Total Dissolved Solids (TDS) concentration 20000mg/L, Cl-At a concentration of 7000mg/L, SO4 2-Has a concentration of 4000Mg/L, Mg2+Has a concentration of 90mg/L, Ca2+Has a concentration of 150mg/L, a concentration of dissolved silicon of 150mg/L, F-Has a concentration of 80mg/L, HCO3 -The concentration of (A) was 500mg/L and the concentration of COD was 120 mg/L.
The method comprises the following specific steps:
step 1, treating the high-salinity wastewater in a high-efficiency hardness removal filtering unit. Firstly, adding calcium hydroxide and magnesium oxide into a primary reaction tank, wherein the adding concentrations are 1.5g/L and 2.0g/L respectively, the reaction time is 30min, the effluent overflows into a secondary reaction tank, sodium carbonate and polyaluminium chloride are added, the adding concentration of the sodium carbonate is 1.8g/L, and the adding concentration of the polyaluminium chloride is 0.3 g/L; then adding sodium hydroxide, adjusting the pH value of the wastewater to 11.5, reacting for 30min, allowing the effluent to enter a primary sedimentation tank to generate hard calcium, hard magnesium, silicates, fluorides and complexes thereof and other various precipitates, and allowing the effluent of the primary sedimentation tank to enter a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.15MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.25 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 200L/m2H is about; the SS of effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is less than 10mg/L, the magnesium ion concentration is less than 10mg/L, the concentration of dissolved silicon is less than 20mg/L, and the concentration of fluorine ions is less than 20 mg/L;
step 2, the high-efficiency hardness removal filtration produced water enters an ozone catalytic oxidation unit for treatment, the ozone catalytic oxidation unit adopts an active carbon-based catalyst, and the operation conditions are as follows: the pH value of the inlet water is 8.5, the inlet water temperature is 30 ℃, the retention time is 2h, and the ozone concentration is 200 mg/L.
Under the condition, COD of the effluent of the ozone catalytic oxidation is about 60 mg/L;
step 3, the effluent of the catalytic oxidation of ozone enters an ultrafiltration unit for treatment, the ultrafiltration unit adopts pressure type ultrafiltration, an external pressure type hollow fiber ultrafiltration membrane component is adopted as the component, and the filtration pressure is 0.12 MPa;
under the condition, the turbidity of the ultrafiltration produced water is less than 0.1 NTU; the concentrated phase of ultrafiltration is treated by centralized transportation after sludge dehydration and solidification;
step 4, the ultrafiltration produced water enters a high-pressure reverse osmosis unit for treatment, the high-pressure reverse osmosis unit adopts a roll type reverse osmosis membrane component, and the operation conditions are as follows: the operating pressure is 6MPa, and the pH value of inlet water is 8.5;
under the condition, the membrane flux of the high-pressure reverse osmosis unit is 10-12L/m2H, the recovery rate of the high-pressure reverse osmosis unit is 50%, and the TDS of the high-pressure reverse osmosis concentrated water is about 40000 mg/L;
and step 5, the high-pressure reverse osmosis concentrated water enters a two-stage nanofiltration unit for treatment, a disc-tube nanofiltration membrane component is adopted in the first-stage nanofiltration in the two-stage nanofiltration unit, and 55% of the first-stage nanofiltration concentrated water returns to the first-stage nanofiltration water inlet and is mixed with inlet water to serve as first-stage nanofiltration inlet water during operation. The operation conditions of the first-stage nanofiltration are as follows: the operation pressure is 4MPa, and the pH value of inlet water is 8.5; the second-stage nanofiltration adopts a roll-type nanofiltration membrane component, and the operating conditions of the second-stage nanofiltration are as follows: the operation pressure is 3MPa, and the pH value of inlet water is 8.5;
under the condition, the membrane flux of the first-stage nanofiltration is 8-10L/m2H, the recovery rate is 70%, and the membrane flux of secondary nanofiltration is 13-15L/m2H, recovery 75%; the mass ratio of chloride ions to sulfate ions in the water produced by the secondary nanofiltration is 60: 1; the mass ratio of sulfate ions to chloride ions in the first-stage nanofiltration concentrated water is 18: 1;
step 6, the water produced by the secondary nanofiltration enters a roll type reverse osmosis unit for treatment, a roll type reverse osmosis membrane component is adopted in roll type reverse osmosis, and the operation conditions are as follows: the operating pressure is 5MPa, and the pH value of inlet water is 8.5;
under the condition, the membrane flux of the roll type reverse osmosis unit is 13-15L/m2H, the recovery rate of the roll-type reverse osmosis unit is 50%;
step 7, the primary nanofiltration concentrated water enters an evaporation crystallization unit for evaporation crystallization treatment to obtain sodium sulfate salts and evaporation crystallization water, and the obtained sodium sulfate salt has the purity of more than 98% after separation and drying and reaches the class II first-class standard in GB/T6009-;
and 8, allowing the rolled reverse osmosis concentrated water to enter an evaporation crystallization unit for evaporation crystallization treatment to obtain sodium chloride salts and evaporation crystallization water, wherein the purity of the obtained sodium chloride salts is over 98% after separation and drying, and the sodium chloride salts reach the primary standard of refined industrial salt in GB/T5462-2015 Industrial salt standard.
Wherein, the water conductivity of the high-pressure reverse osmosis produced water, the spiral reverse osmosis produced water and the evaporative crystallization produced water after being mixed is less than 1200 mu S/cm, the COD is less than 60mg/L, and the Cl is-Less than 200mg/L, and meets the water replenishing and recycling requirements of recycled circulating water.
Example 4 (comparative)
Example 4 was set up essentially the same as example 3, except that step 1 of example 4 was:
firstly, adding sodium carbonate, sodium hydroxide and polyaluminium chloride into a primary reaction tank, wherein the concentration of the sodium carbonate is 1.8g/L, the pH of the wastewater is adjusted to 11.5 by the sodium hydroxide, the concentration of the polyaluminium chloride is 0.3g/L, the reaction time is 30min, effluent enters a primary sedimentation tank to generate various precipitates such as hard calcium, hard magnesium, silicates, fluorides and complexes thereof, and the effluent of the primary sedimentation tank enters a filtering unit to form high-efficiency hard removal filtered water; the filtering pressure of the membrane filtering unit is 0.15MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.25 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 200L/m2H is about; the SS of the effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is about 10mg/L, the magnesium ion concentration is about 10mg/L, and the concentration of dissolved silicon and fluorine ions is higher than that of the effluentHigh, the concentration of the silicon dissolved out of water is about 90mg/L, and the concentration of the fluorinion is about 55 mg/L. The removal effect of the discharged water-soluble silicon and fluorine ions is poor, the subsequent treatment requirement cannot be met, the evaporation crystallizer is seriously corroded due to the high fluorine ions, the subsequent system is scaled due to the dissolved silicon, and the stable operation cannot be realized.
Example 5 (comparative)
Example 5 was set up essentially the same as example 3, except that step 1 of example 5 was:
firstly, adding calcium hydroxide, sodium carbonate and polyaluminium chloride into a primary reaction tank, wherein the adding amount of the calcium hydroxide is that the pH value of the wastewater is adjusted to be 11.5, the adding concentration of the sodium carbonate is 1.8g/L, and the adding concentration of the polyaluminium chloride is 0.3 g/L; the reaction time is 30min, the effluent enters a primary sedimentation tank to generate various precipitates such as hard calcium, hard magnesium, silicate, fluoride and complex compounds thereof, and the effluent of the primary sedimentation tank enters a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.15MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.25 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 200L/m2H is about; the SS of the effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is about 10mg/L, the magnesium ion concentration is about 10mg/L, the concentration of dissolved silicon and fluorine ions is higher, the concentration of the dissolved silicon in the effluent is about 90mg/L, and the concentration of the fluorine ions is about 45 mg/L. The removal effect of the discharged water-soluble silicon and fluorine ions is poor, the subsequent treatment requirement cannot be met, the evaporation crystallizer is seriously corroded due to the high fluorine ions, the subsequent system is scaled due to the dissolved silicon, and the stable operation cannot be realized.
Example 6 (comparative)
Example 6 was set up essentially the same as example 3, except that step 1 of example 6 was:
step 1, treating the high-salinity wastewater in a high-efficiency hardness removal filtering unit. Firstly, adding calcium hydroxide and magnesium oxide into a first-stage reaction tank, wherein the adding concentrations are 1.5g/L and 2.0g/L respectively; then adding sodium carbonate and polyaluminium chloride, wherein the concentration of the sodium carbonate is 1.8g/L, and the concentration of the polyaluminium chloride is 0.3 g/L; then adding sodium hydroxide, adjusting the pH value of the wastewater to 11.5, reacting for 30min, allowing the effluent to enter a primary sedimentation tank to generate hard calcium, hard magnesium, silicates, fluorides and complexes thereof and other various precipitates, and allowing the effluent of the primary sedimentation tank to enter a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.15MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.25 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 200L/m2H is about; the SS of effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is about 10mg/L, the magnesium ion concentration is about 10mg/L, the silicon concentration of effluent solution is about 30mg/L, and the fluorine ion concentration is about 35 mg/L. The removal effect of the discharged water-soluble silicon and fluorine ions is poor, the higher fluorine ions can cause the serious corrosion of an evaporation crystallizer, the higher silicon-soluble ions can also cause the scaling of a subsequent system, and the cleaning period of the subsequent system is shortened. In fact, researches show that under the condition of the same water quality, the two-stage reaction dosing is adopted, so that the dosing amount of the medicament is saved compared with the one-stage dosing, the dosing cost of the medicament is saved, and meanwhile, the subsequent sludge treatment cost is indirectly reduced.
Comparative example 1
Comparative example 1 was set up substantially the same as example 3, except that comparative example 1 used only a first nanofiltration unit and not a second nanofiltration unit, and the specific steps included:
step 1, treating the high-salinity wastewater in a high-efficiency hardness removal filtering unit. Firstly, adding calcium hydroxide and magnesium oxide into a primary reaction tank, wherein the adding concentrations are 1.5g/L and 2.0g/L respectively, the reaction time is 30min, the effluent overflows into a secondary reaction tank, sodium carbonate and polyaluminium chloride are added, the adding concentration of the sodium carbonate is 1.8g/L, and the adding concentration of the polyaluminium chloride is 0.3 g/L; then adding sodium hydroxide, adjusting the pH value of the wastewater to 11.5, reacting for 30min, allowing the effluent to enter a primary sedimentation tank to generate hard calcium, hard magnesium, silicates, fluorides and complexes thereof and other various precipitates, and allowing the effluent of the primary sedimentation tank to enter a filtering unit to form high-efficiency hardness-removing filtered effluent; the filtering pressure of the membrane filtering unit is 0.15MPa, the membrane material is polytetrafluoroethylene, and the membrane aperture is 0.25 mu m; solidifying the filter residues and then carrying out centralized treatment;
under the condition, the membrane flux of the membrane filtration unit is controlled at 200L/m2H is about; the SS of effluent of the membrane filtration unit is less than 0.5mg/L, the calcium ion concentration of the effluent is less than 10mg/L, the magnesium ion concentration is less than 10mg/L, the concentration of dissolved silicon is less than 20mg/L, and the concentration of fluorine ions is less than 20 mg/L;
step 2, the high-efficiency hardness removal filtration produced water enters an ozone catalytic oxidation unit for treatment, the ozone catalytic oxidation unit adopts an active carbon-based catalyst, and the operation conditions are as follows: the pH value of the inlet water is 8.5, the inlet water temperature is 30 ℃, the retention time is 2h, and the ozone concentration is 200 mg/L.
Under the condition, COD of the effluent of the ozone catalytic oxidation is about 60 mg/L;
step 3, the effluent of the catalytic oxidation of ozone enters an ultrafiltration unit for treatment, the ultrafiltration unit adopts pressure type ultrafiltration, an external pressure type hollow fiber ultrafiltration membrane component is adopted as the component, and the filtration pressure is 0.12 MPa;
under the condition, the turbidity of the ultrafiltration produced water is less than 0.1 NTU; the concentrated phase of ultrafiltration is treated by centralized transportation after sludge dehydration and solidification;
step 4, the ultrafiltration produced water enters a high-pressure reverse osmosis unit for treatment, the high-pressure reverse osmosis unit adopts a roll type reverse osmosis membrane component, and the operation conditions are as follows: the operating pressure is 6MPa, and the pH value of inlet water is 8.5;
under the condition, the membrane flux of the high-pressure reverse osmosis unit is 10-12L/m2H, the recovery rate of the high-pressure reverse osmosis unit is 50%, and the TDS of the high-pressure reverse osmosis concentrated water is about 40000 mg/L;
and step 5, the high-pressure reverse osmosis concentrated water enters a first-stage nanofiltration unit for treatment, a disc-tube nanofiltration membrane component is adopted in first-stage nanofiltration, and when the device is operated, 55% of first-stage nanofiltration concentrated water returns to a first-stage nanofiltration water inlet and is mixed with inlet water to serve as first-stage nanofiltration inlet water. The operation conditions of the first-stage nanofiltration are as follows: the operation pressure is 4MPa, and the pH value of inlet water is 8.5; under the condition, the membrane flux of the first-stage nanofiltration is 8-10L/m2H, the recovery rate is 70%, and the mass ratio of chloride ions to sulfate ions in the first-stage nanofiltration produced water is 35: 1; the mass ratio of sulfate ions to chloride ions in the first-stage nanofiltration concentrated water is 10: 1;
step 6, the first-stage nanofiltration produced water enters a roll type reverse osmosis unit for treatment, a roll type reverse osmosis membrane component is adopted in roll type reverse osmosis, and the operation conditions are as follows: the operating pressure is 5MPa, and the pH value of inlet water is 8.5;
under the condition, the membrane flux of the roll type reverse osmosis unit is 12-14L/m2H, the recovery rate of the roll-type reverse osmosis unit is 50%;
step 7, the first-stage nanofiltration concentrated water enters an evaporation crystallization unit to be subjected to evaporation crystallization treatment to obtain sodium sulfate and evaporation crystallization water, and the obtained sodium sulfate is separated and dried to have the purity of about 80%;
and 8, allowing the rolled reverse osmosis concentrated water to enter an evaporation crystallization unit for evaporation crystallization treatment to obtain sodium chloride salts and evaporation crystallization produced water, and separating and drying the obtained sodium chloride salts to obtain the sodium chloride with the purity of about 88%.
Wherein, the water conductivity of the high-pressure reverse osmosis produced water, the spiral reverse osmosis produced water and the evaporative crystallization produced water after being mixed is less than 1200 mu S/cm, the COD is less than 60mg/L, and the Cl is-Less than 200mg/L, and meets the water replenishing and recycling requirements of recycled circulating water.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A resourceful treatment device for high-salinity wastewater comprises: the device comprises a hard removal filtering unit, an ozone catalytic oxidation unit, an ultrafiltration unit, a high-pressure reverse osmosis unit, a primary nanofiltration unit, a secondary nanofiltration unit, a roll type reverse osmosis unit, a first evaporative crystallization unit and a second evaporative crystallization unit;
the system comprises a hard-removing filtering unit, an ozone catalytic oxidation unit, a first-stage nanofiltration unit, a second-stage nanofiltration unit and a second-stage nanofiltration unit, wherein a water producing port of the hard-removing filtering unit is connected with a water inlet of the ozone catalytic oxidation unit, a water outlet of the ozone catalytic oxidation unit is connected with a water inlet of the ultrafiltration unit, a water producing port of the ultrafiltration unit is connected with a water inlet of the high-pressure reverse osmosis unit, a concentrated water outlet of the high-pressure reverse osmosis unit is connected with a water inlet of the first-stage nanofiltration unit, a concentrated water outlet of the first-stage nanofiltration unit is connected with a water inlet of the first-stage nanofiltration unit, a concentrated water outlet of the second-stage nanofiltration unit is connected with a water inlet of the roll-type reverse osmosis unit, and a concentrated water outlet of the roll-type reverse osmosis unit is connected with a water inlet of the second-stage nanofiltration unit; preferably, a concentrated water outlet of the secondary nanofiltration unit is connected with a water inlet of the primary nanofiltration unit.
2. The resource treatment device according to claim 1, wherein the hardness removal and filtration unit comprises a primary reaction tank, a secondary reaction tank, a primary sedimentation tank and a filtration device, wherein a partition plate is arranged between the primary reaction tank and the secondary reaction tank, a water outlet of the secondary reaction tank is connected with a water inlet of the primary sedimentation tank, and a water outlet of the primary sedimentation tank is connected with a water inlet of the filtration device; preferably, the first-stage reaction tank is provided with soluble calcium salt dosing equipment and magnesium agent dosing equipment, and the second-stage reaction tank is provided with sodium carbonate dosing equipment, flocculating agent dosing equipment and sodium hydroxide dosing equipment.
3. The resource treatment device according to claim 1 or 2, wherein the first-stage nanofiltration unit adopts a disc-tube nanofiltration membrane component; and/or the second-stage nanofiltration unit adopts a roll-type nanofiltration membrane component.
4. A method for treating high-salinity wastewater in coal chemical industry by using the resource treatment device according to any one of claims 1 to 3, comprising the following steps:
s1, introducing high-salinity wastewater into the hardness-removing filtering unit to form a filtering concentrated phase and filtering produced water;
s2, introducing the filtered produced water into the ozone catalytic oxidation unit to form ozone catalytic oxidation effluent;
s3, introducing the effluent of the catalytic oxidation of ozone into the ultrafiltration unit to form ultrafiltration water;
s4, introducing the ultrafiltration produced water into the high-pressure reverse osmosis unit to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water;
s5, introducing the high-pressure reverse osmosis concentrated water into the primary nanofiltration unit to form primary nanofiltration concentrated water and primary nanofiltration produced water;
s6, introducing the primary nanofiltration concentrated water into the first evaporative crystallization unit to obtain sodium sulfate solid and first evaporative crystallization water;
s7, introducing the primary nanofiltration water product into the secondary nanofiltration unit to obtain secondary nanofiltration concentrated water and secondary nanofiltration water product;
s8, introducing the secondary nanofiltration produced water into the roll type reverse osmosis unit to obtain roll type reverse osmosis produced water and roll type reverse osmosis concentrated water, and preferably introducing the secondary nanofiltration concentrated water into the primary nanofiltration unit;
and S9, introducing the rolled reverse osmosis concentrated water into the second evaporative crystallization unit to obtain sodium chloride solid and second evaporative crystallization water.
5. The method according to claim 4, wherein step S1 includes:
a) introducing the high-salinity wastewater into the primary reaction tank, and adding soluble calcium salt and a magnesium agent into the primary reaction tank;
b) overflowing the effluent of the primary reaction tank to the secondary reaction tank, adding sodium carbonate, a flocculating agent and sodium hydroxide into the primary reaction tank, preferably adding the sodium carbonate and the flocculating agent first, and then adding the sodium hydroxide;
c) the effluent of the secondary reaction tank enters the primary sedimentation tank;
d) passing the primary clarifier effluent into the filtration unit, thereby forming the filtered concentrate phase and the filtered product water;
preferably, the soluble calcium salt is calcium chloride and/or calcium hydroxide; the magnesium agent is selected from one or more of magnesium oxide, magnesium chloride and magnesium sulfate; the flocculating agent is selected from polyaluminium chloride and/or polyferric sulfate;
more preferably, the soluble calcium salt is added in an amount of 0.8 to 1.5g per increased salt content of the wastewater; and/or the addition amount of the magnesium agent is 0.8g to 2.0 g; and/or the addition amount of the sodium carbonate is 1.0 g-1.8 g; and/or the addition amount of the flocculating agent is 0.1 g-0.3 g; and/or the addition amount of the sodium hydroxide is such that the pH value of the high-salinity wastewater in the secondary reaction tank is 10.5-11.5;
more preferably, the membrane material adopted by the filtering device is a polytetrafluoroethylene membrane, preferably the polytetrafluoroethylene membrane with the membrane pore size of 0.15-0.25 μm, more preferably the filtering pressure of the filtering device is 0.08-0.15 MPa, and the membrane flux is 200L/m2·h～400L/m2·h。
6. The method according to claim 4 or 5, wherein the water quality characteristics of the coal chemical industry high-salinity wastewater are as follows: the pH value is 7.5-8.5; and/or the total soluble solid concentration is 10000 mg/L-20000 mg/L; and/or Cl-The concentration is 4000 mg/L-7000 mg/L; and/or SO4 2-The concentration is 2000 mg/L-4000 mg/L; and/or Mg2+The concentration is 30 mg/L-90 mg/L; and/or Ca2+The concentration is 50 mg/L-150 mg/L; and/or the concentration of dissolved silicon is 50 mg/L-150 mg/L; and/or F-The concentration is 50 mg/L-80 mg/L; and/or HCO3 -The concentration is 300 mg/L-500 mg/L; and/or the chemical oxygen demand is 80 mg/L-120 mg/L.
7. The method according to any one of claims 4 to 6,
in step S2, the ozone catalytic oxidation unit employs an activated carbon-based catalyst; and/or the operating conditions of the ozone catalytic oxidation unit comprise: the pH value of the inlet water is 7.0-9.0, preferably 7.5-8.5, and/or the inlet water temperature is 5-35 ℃, preferably 15-30 ℃, and/or the residence time is 0.1-5 h, preferably 1-2 h, and/or the ozone concentration is 100-250 mg/L, preferably 150-200 mg/L; and/or
In step S3, the operating conditions of the ultrafiltration unit include: the filtering pressure is 0.05MPa to 0.15MPa, preferably 0.08MPa to 0.12 MPa; and/or
In step S4, the operating conditions of the high pressure reverse osmosis unit include: the operation pressure is 1MPa to 10MPa, preferably 4MPa to 6MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 5L/m2·h～20L/m2H, preferably 10L/m2·h～15L/m2H and/or a recovery rate of 40% to 70%, preferably 50% to 60%.
8. The method according to any one of claims 4 to 7,
in step S5, the operating conditions of the primary nanofiltration unit include: the operation pressure is 1MPa to 5MPa, preferably 3MPa to 4MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 5L/m2·h～20L/m2H, preferably 8L/m2·h～15L/m2H, and/or a recovery rate of 65% to 80%, preferably 70% to 65%; and/or
In step S7, the operating conditions of the secondary nanofiltration unit include: the operation pressure is 1MPa to 5MPa, preferably 2MPa to 3MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 10L/m2·h～25L/m2H, preferably 13L/m2·h～20L/m2H and/or a recovery rate of 70% to 85%, preferably 75% to 80%.
9. The method according to any one of claims 4 to 8, wherein the mass ratio of chloride ions to sulfate ions in the secondary nanofiltration product water is (50-70: 1, preferably (55-60: 1); and/or the mass ratio of sulfate ions to chloride ions in the primary nanofiltration concentrated water is (10-20): 1, preferably (15-18): 1.
10. The method according to any of claims 4-9, wherein in step S8, the operating conditions of the roll-to-roll reverse osmosis unit comprise: the operation pressure is 1MPa to 10MPa, preferably 3MPa to 5MPa, and/or the pH of inlet water is 7.0 to 9.0, preferably 7.5 to 8.5, and/or the membrane flux is 10L/m2·h～25L/m2H, preferably 13L/m2·h～18L/m2H and/or a recovery rate of 40% to 70%, preferably 50% to 60%.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004261474A1 (en) * | 2003-07-30 | 2005-02-10 | Surrey Aquatechnology Limited | Solvent removal process |
| CN105060650A (en) * | 2015-08-25 | 2015-11-18 | 格蓝特环保工程(北京)有限公司 | Sewage resourcesization treatment method |
| CN107651794A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院过程工程研究所 | A kind of processing system and processing method of industrial wastewater bio-chemical effluent |
| CN108529802A (en) * | 2018-04-03 | 2018-09-14 | 山东玉鑫环保科技股份有限公司 | Titanium white production discharges high slat-containing wastewater zero-emission technique |
| WO2019159197A1 (en) * | 2018-02-15 | 2019-08-22 | S P Textile Processors Pvt. Ltd. | Method and apparatus for regenerating a working salt solution in salt purification |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN110902923A (en) * | 2019-12-04 | 2020-03-24 | 安徽普朗膜技术有限公司 | Treatment and recovery system for high-salinity wastewater in coal chemical industry |
-
2020
- 2020-09-07 CN CN202010929041.4A patent/CN114149113A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004261474A1 (en) * | 2003-07-30 | 2005-02-10 | Surrey Aquatechnology Limited | Solvent removal process |
| CN105060650A (en) * | 2015-08-25 | 2015-11-18 | 格蓝特环保工程(北京)有限公司 | Sewage resourcesization treatment method |
| CN107651794A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院过程工程研究所 | A kind of processing system and processing method of industrial wastewater bio-chemical effluent |
| WO2019159197A1 (en) * | 2018-02-15 | 2019-08-22 | S P Textile Processors Pvt. Ltd. | Method and apparatus for regenerating a working salt solution in salt purification |
| CN108529802A (en) * | 2018-04-03 | 2018-09-14 | 山东玉鑫环保科技股份有限公司 | Titanium white production discharges high slat-containing wastewater zero-emission technique |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN110902923A (en) * | 2019-12-04 | 2020-03-24 | 安徽普朗膜技术有限公司 | Treatment and recovery system for high-salinity wastewater in coal chemical industry |
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