CN114772823B - Evaporation mother liquor treatment system and process - Google Patents
Evaporation mother liquor treatment system and process Download PDFInfo
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- CN114772823B CN114772823B CN202210333876.2A CN202210333876A CN114772823B CN 114772823 B CN114772823 B CN 114772823B CN 202210333876 A CN202210333876 A CN 202210333876A CN 114772823 B CN114772823 B CN 114772823B
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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
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01D3/04—Chlorides
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- 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
- C01D3/14—Purification
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- 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
- C01D5/16—Purification
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/16—Purification
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/22—Treatment of water, waste water, or sewage by freezing
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- 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
- C02F1/5281—Installations for water purification using chemical agents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
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Abstract
An evaporation mother liquor treatment system and process, the system removes the hard and removes the impurity unit and carries on the preconditioning of purification to the evaporation mother liquor received; the first dilution unit dilutes the evaporation mother liquor after the purification pretreatment; the filtration unit filters the evaporated mother liquor diluted by the first dilution unit; the nanofiltration membrane concentration unit separates monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank caches concentrated water of the nanofiltration membrane concentration unit; the freezing recrystallization unit carries out freezing recrystallization on the concentrated water in the nanofiltration concentrated water tank; the nanofiltration water production tank caches the water produced by the nanofiltration membrane concentration unit; the evaporation crystallization unit performs evaporation crystallization on the received water produced by the nanofiltration water production tank; the second dilution unit dilutes the received concentrated solution of the evaporative crystallization unit, and the selective membrane salt separation unit performs monovalent salt separation on the received diluted solution of the second dilution unit. The invention has wider applicability and stable performance; can effectively treat the evaporation mother liquor, realize the reclamation of mixed salt and reduce the treatment cost.
Description
Technical Field
The invention relates to an evaporation mother liquor treatment system and an evaporation mother liquor treatment process, and belongs to the technical field of water treatment.
Background
In recent years, zero emission of water treatment has been a trend, and industries such as coal chemical industry, power plants, mine water and the like have begun to implement zero emission of sewage. In the zero emission project, the evaporation process is indispensable, and a large amount of evaporation mother liquor is generated in the evaporation process, and the main components of the evaporation mother liquor are sodium nitrate, sodium chloride and sodium sulfate mixed solution.
Common evaporation mother liquor treatment modes are as follows: the evaporated mother liquor is sent to a professional mother liquor treatment center or is added with a curing agent (lime and the like) to be cured and then is used as hazardous waste for landfill; there are also schemes for incinerating the mother liquor. Due to the characteristics of high COD and high salinity of the evaporation mother liquor, the treatment cost is extremely high, the content of the high COD and heavy metal is high, the harm to the environment is extremely great, and the treatment difficulty is high. How to realize the low-cost recycling treatment of the evaporation mother liquor is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an evaporation mother liquor treatment system and an evaporation mother liquor treatment process, which solve the problems of high treatment cost, high difficulty and incapability of realizing the resource treatment of mixed salt in the traditional evaporation mother liquor treatment.
The technical scheme for solving the technical problems is as follows: an evaporation mother liquor treatment system comprises a hard removal impurity removal unit, a first dilution unit, a filtering unit, a nanofiltration membrane concentration unit, a nanofiltration concentrate tank, a freezing recrystallization unit, a nanofiltration product tank, an evaporation crystallization unit, a second dilution unit and a selective membrane salt separation unit;
the hard removing and impurity removing unit is connected with the first dilution unit through a conveying pipeline and is used for purifying and preprocessing the received evaporation mother liquor;
the first dilution unit is connected with the filtering unit through a conveying pipeline and is used for diluting the evaporation mother liquor after the received purification pretreatment of the hard removal and impurity removal unit;
the filtering unit is connected with the nanofiltration membrane concentration unit through a conveying pipeline and is used for filtering the received evaporation mother liquor diluted by the first dilution unit;
the nanofiltration membrane concentration unit is used for separating monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank is connected with the freezing recrystallization unit through a conveying pipeline and is used for caching the received concentrated water of the nanofiltration membrane concentration unit; the freezing recrystallization unit is used for freezing and recrystallizing the received concentrated water in the nanofiltration concentrated water tank;
the water outlet of the nanofiltration membrane concentration unit is connected with the nanofiltration water production tank through a conveying pipeline, the nanofiltration water production tank is connected with the evaporation crystallization unit through a conveying pipeline, and the nanofiltration water production tank is used for caching the received water produced by the nanofiltration membrane concentration unit; the evaporation port of the evaporation crystallization unit is connected with the second dilution unit through a conveying pipeline, and the evaporation crystallization unit is used for performing evaporation crystallization on the received produced water of the nanofiltration water production tank; the second dilution unit is connected with the selective membrane salt separation unit through a conveying pipeline, the second dilution unit is used for diluting the received concentrated solution of the evaporative crystallization unit, and the selective membrane salt separation unit is used for monovalent salt separation of the received diluted solution of the second dilution unit.
As a preferred scheme of the evaporation mother liquor treatment system, the evaporation mother liquor treatment system further comprises a first drying unit, wherein the freezing recrystallization unit is connected with the first drying unit through a conveying pipeline, and the first drying unit is used for drying the received product of the freezing recrystallization unit to obtain anhydrous sodium sulfate.
As a preferred scheme of the evaporation mother liquor treatment system, the evaporation mother liquor treatment system further comprises a second drying unit, wherein the second drying unit is connected with the evaporation crystallization unit through a conveying pipeline and is used for drying the received product of the evaporation crystallization unit to obtain sodium chloride.
As the preferable scheme of the evaporation mother liquor treatment system, the concentrated water port of the selective membrane salt separation unit is connected with the nanofiltration water production tank through a return pipeline;
the water outlet of the selective membrane salt separation unit is connected with a salt separation water production tank through a conveying pipeline, and the salt separation water production tank is used for caching the received water produced by the selective membrane salt separation unit.
As the preferable scheme of evaporation mother liquor treatment system, divide salt to produce the water tank and be connected with evaporation concentration unit through the transfer line, evaporation concentration unit is used for carrying out evaporation concentration to the water that divides salt to produce the water tank that receives.
As the preferred scheme of evaporation mother liquor processing system, evaporation concentration unit is connected with the cooling unit through the transfer line, the cooling unit is used for carrying out the cooling to the concentrated aqueous solution of evaporation concentration unit of receipt in order to precipitate sodium nitrate crystal.
As the preferable scheme of evaporation mother liquor treatment system, the cooling unit is connected with a third drying unit through a conveying pipeline, and the third drying unit is used for drying the sodium nitrate crystal separated out by the cooling unit.
As the preferred scheme of evaporation mother liquor treatment system, still include the comdenstion water tank, freezing recrystallization unit the evaporation crystallization unit with evaporation concentration unit all is through transfer line connection comdenstion water tank, comdenstion water tank is used for receiving the freezing recrystallization unit the evaporation crystallization unit with the condensate that evaporation concentration unit produced.
The invention also provides an evaporation mother liquor treatment process, which adopts the evaporation mother liquor treatment system and comprises the following steps:
conveying the evaporation mother liquor containing sodium nitrate, sodium chloride and sodium sulfate to a hard removing and impurity removing unit, and purifying and preprocessing the received evaporation mother liquor through the hard removing and impurity removing unit;
the evaporation mother liquor after the purification pretreatment of the hard and impurity removal unit is conveyed to a first dilution unit, and the first dilution unit dilutes the received evaporation mother liquor after the purification pretreatment of the hard and impurity removal unit;
the evaporation mother liquor diluted by the first dilution unit is conveyed to a filtering unit, and the received evaporation mother liquor diluted by the first dilution unit is filtered by the filtering unit;
delivering the evaporation mother liquor filtered by the filtering unit to a nanofiltration membrane concentration unit, separating monovalent salt from divalent salt from the received evaporation mother liquor by the nanofiltration membrane concentration unit, delivering concentrated water at a concentrated water port of the nanofiltration membrane concentration unit to a nanofiltration concentrated water tank for caching, delivering concentrated water cached by the nanofiltration concentrated water tank to a freezing recrystallization unit, and freezing and recrystallizing the received concentrated water of the nanofiltration concentrated water tank by the freezing recrystallization unit;
and conveying water produced at a water producing port of the nanofiltration membrane concentration unit to a nanofiltration water producing tank for caching, conveying the water produced cached in the nanofiltration water producing tank to an evaporation crystallization unit, performing evaporation crystallization on the received water produced in the nanofiltration water producing tank through the evaporation crystallization unit, conveying evaporation liquid at an evaporation port of the evaporation crystallization unit to a second dilution unit for dilution, and conveying the diluted dilution liquid to a selective membrane salt separation unit for monovalent salt separation.
As a preferred option of the evaporation mother liquor treatment process, the product of the freeze-recrystallization unit is conveyed to a first drying unit, through which the received product of the freeze-recrystallization unit is dried to obtain anhydrous sodium sulfate.
As a preferred embodiment of the process for treating the evaporation mother liquor, the product of the evaporation crystallization unit is transferred to a second drying unit, and the received product of the evaporation crystallization unit is dried by the second drying unit to obtain sodium chloride.
As the preferable scheme of the evaporation mother liquor treatment process, the concentrated water at the concentrated water port of the selective membrane salt separation unit is returned to the nanofiltration water production tank through a return pipeline.
As the preferable scheme of the evaporation mother liquor treatment process, the water produced at the water producing port of the selective membrane salt separating unit is conveyed to a salt separating water producing tank for buffering; delivering the produced water buffered by the salt separating water producing tank to an evaporation concentration unit, and performing evaporation concentration on the received produced water of the salt separating water producing tank through the evaporation concentration unit;
conveying the concentrated water liquid of the evaporation concentration unit to a cooling unit, and cooling the received concentrated water liquid of the evaporation concentration unit by the cooling unit to separate out sodium nitrate crystals;
and conveying the sodium nitrate crystals separated out by the cooling unit to a third drying unit, and drying the sodium nitrate crystals separated out by the cooling unit through the third drying unit.
As the preferable scheme of the evaporation mother liquor treatment process, the condensate liquid of the freezing recrystallization unit, the evaporation crystallization unit and the evaporation concentration unit is conveyed to a condensate water tank for caching.
The invention is provided with a hard removing and impurity removing unit, a first dilution unit, a filtering unit, a nanofiltration membrane concentration unit, a nanofiltration concentrate water tank, a freezing recrystallization unit, a nanofiltration water production tank, an evaporation crystallization unit, a second dilution unit and a selective membrane salt separating unit; the hard removing and impurity removing unit is connected with the first dilution unit through a conveying pipeline and is used for purifying and preprocessing the received evaporation mother liquor; the first dilution unit is connected with the filtering unit through a conveying pipeline and is used for diluting the evaporation mother liquor after the received purification pretreatment of the hard removal and impurity removal unit; the filtering unit is connected with the nanofiltration membrane concentration unit through a conveying pipeline and is used for filtering the evaporation mother liquor diluted by the received first dilution unit; the nanofiltration membrane concentration unit is used for separating monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank is connected with the freezing recrystallization unit through a conveying pipeline and is used for caching the received concentrated water of the nanofiltration membrane concentration unit; the freezing recrystallization unit is used for freezing and recrystallizing the concentrated water in the received nanofiltration concentrated water tank; the water producing port of the nanofiltration membrane concentration unit is connected with a filtration water producing tank through a conveying pipeline, the nanofiltration water producing tank is connected with an evaporation crystallization unit through the conveying pipeline, and the nanofiltration water producing tank is used for caching the received water produced by the nanofiltration membrane concentration unit; the evaporation port of the evaporation crystallization unit is connected with the second dilution unit through a conveying pipeline, and the evaporation crystallization unit is used for performing evaporation crystallization on the received water produced by the nanofiltration water production tank; the second dilution unit is connected with the selective membrane salt separation unit through a conveying pipeline, the second dilution unit is used for diluting the received concentrated solution of the evaporative crystallization unit, and the selective membrane salt separation unit is used for carrying out monovalent salt separation on the received diluted solution of the second dilution unit. The nanofiltration membrane concentration unit is adopted, the open fluid channel is wide in flowing, the self-cleaning effect is excellent, the pressure loss is reduced by the vortex rotating flow channel, the applicability is wider, complex pretreatment is not needed, and the performance is more stable; the separation of the impurity salts (monovalent salt and multivalent salt) in the evaporation mother liquor can be realized; the evaporation mother liquor can be effectively treated, so that the problem of high nitrate concentration is solved; realizes the reclamation of the mixed salt, finishes the process of changing waste into valuable, reduces the treatment cost and truly realizes the economic benefit and the social benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
The structures, proportions, sizes, etc. shown in the present specification are shown only for the purposes of illustration and description, and are not intended to limit the scope of the invention, which is defined by the claims, so that any structural modifications, changes in proportions, or adjustments of sizes, which do not affect the efficacy or the achievement of the present invention, should fall within the ambit of the technical disclosure.
FIG. 1 is a schematic diagram of an evaporation mother liquor treatment system provided in an embodiment of the present invention;
fig. 2 is a schematic diagram of an evaporation mother liquor treatment process according to an embodiment of the present invention.
In the figure, 1, a hard and impurity removing unit; 2. a first dilution unit; 3. a filtering unit; 4. a nanofiltration membrane concentration unit; 5. nanofiltration concentrated water tank; 6. a freeze recrystallization unit; 7. a nanofiltration water tank; 8. an evaporation crystallization unit; 9. a second dilution unit; 10. a selective membrane salination unit; 11. a first drying unit; 12. a second drying unit; 13. salt separating water producing tank; 14. an evaporation concentration unit; 15. a cooling unit for cooling; 16. a third drying unit; 17. a condensed water tank.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides an evaporation mother liquor treatment system, which includes a hard removal impurity removal unit 1, a first dilution unit 2, a filtration unit 3, a nanofiltration membrane concentration unit 4, a nanofiltration concentrate water tank 5, a freeze recrystallization unit 6, a nanofiltration product water tank 7, an evaporation crystallization unit 8, a second dilution unit 9, and a selective membrane salt separation unit 10;
the hard removing and impurity removing unit 1 is connected with the first dilution unit 2 through a conveying pipeline, and the hard removing and impurity removing unit 1 is used for purifying and preprocessing the received evaporation mother liquor;
the first dilution unit 2 is connected with the filtering unit 3 through a conveying pipeline, and the first dilution unit 2 is used for diluting the evaporation mother liquor after the received purification pretreatment of the hard removal and impurity removal unit 1;
the filtering unit 3 is connected with the nanofiltration membrane concentration unit 4 through a conveying pipeline, and the filtering unit 3 is used for filtering the received evaporation mother liquor diluted by the first dilution unit 2;
the concentrated water port of the nanofiltration membrane concentration unit 4 is connected with the nanofiltration concentrated water tank 5 through a conveying pipeline, and the nanofiltration membrane concentration unit 4 is used for separating monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank 5 is connected with the freezing recrystallization unit 6 through a conveying pipeline, and the nanofiltration concentrated water tank 5 is used for caching the received concentrated water of the nanofiltration membrane concentration unit 4; the freezing and recrystallizing unit 6 is used for freezing and recrystallizing the received concentrated water in the nanofiltration concentrated water tank 5;
the water outlet of the nanofiltration membrane concentration unit 4 is connected with the nanofiltration water production tank 7 through a conveying pipeline, the nanofiltration water production tank 7 is connected with the evaporation crystallization unit 8 through a conveying pipeline, and the nanofiltration water production tank 7 is used for caching the received water produced by the nanofiltration membrane concentration unit 4; the evaporation port of the evaporation crystallization unit 8 is connected with the second dilution unit 9 through a conveying pipeline, and the evaporation crystallization unit 8 is used for performing evaporation crystallization on the received produced water of the nanofiltration produced water tank 7; the second dilution unit 9 is connected with the selective membrane salt separation unit 10 through a conveying pipeline, the second dilution unit 9 is used for diluting the received concentrated solution of the evaporative crystallization unit 8, and the selective membrane salt separation unit 10 is used for carrying out monovalent salt separation on the received diluted solution of the second dilution unit 9.
In this embodiment, the apparatus further includes a first drying unit 11, the freeze-recrystallization unit 6 is connected to the first drying unit 11 through a conveying pipeline, and the first drying unit 11 is configured to dry the received product of the freeze-recrystallization unit 6 to obtain anhydrous sodium sulfate. And a second drying unit 12, wherein the second drying unit 12 is connected with the evaporative crystallization unit 8 through a conveying pipeline, and the second drying unit 12 is used for drying the received product of the evaporative crystallization unit 8 to obtain sodium chloride. The water concentration port of the selective membrane salt separation unit 10 is connected with the nanofiltration water production tank 7 through a return pipeline; the water outlet of the selective membrane salt separation unit 10 is connected with a salt separation water production tank 13 through a conveying pipeline, and the salt separation water production tank 13 is used for caching the received water produced by the selective membrane salt separation unit 10. The salt separating water producing tank 13 is connected with an evaporation concentration unit 14 through a conveying pipeline, and the evaporation concentration unit 14 is used for performing evaporation concentration on the received produced water of the salt separating water producing tank 13. The evaporation and concentration unit 14 is connected with a cooling unit 15 through a conveying pipeline, and the cooling unit 15 is used for cooling the received concentrated water solution of the evaporation and concentration unit 14 so as to separate out sodium nitrate crystals. The cooling and cooling unit 15 is connected with a third drying unit 16 through a conveying pipeline, and the third drying unit 16 is used for drying the sodium nitrate crystals separated out by the cooling and cooling unit 15. The device further comprises a condensed water tank 17, wherein the freezing recrystallization unit 6, the evaporation crystallization unit 8 and the evaporation concentration unit 14 are all connected with the condensed water tank 17 through conveying pipelines, and the condensed water tank 17 is used for receiving condensate generated by the freezing recrystallization unit 6, the evaporation crystallization unit 8 and the evaporation concentration unit 14.
Referring to fig. 2, the invention further provides an evaporation mother liquor treatment process, which adopts the evaporation mother liquor treatment system, and comprises the following steps:
the method comprises the steps of conveying an evaporation mother liquor containing sodium nitrate, sodium chloride and sodium sulfate to a hard removing and impurity removing unit 1, and purifying and preprocessing the received evaporation mother liquor through the hard removing and impurity removing unit 1;
the evaporation mother liquor after the purification pretreatment of the hard removal and impurity removal unit 1 is conveyed to a first dilution unit 2, and the first dilution unit 2 dilutes the received evaporation mother liquor after the purification pretreatment of the hard removal and impurity removal unit 1;
the evaporation mother liquor diluted by the first dilution unit 2 is conveyed to a filtering unit 3, and the received evaporation mother liquor diluted by the first dilution unit 2 is filtered by the filtering unit 3;
the evaporation mother liquor filtered by the filtering unit 3 is conveyed to a nanofiltration membrane concentration unit 4, monovalent salt and divalent salt are separated from the received evaporation mother liquor through the nanofiltration membrane concentration unit 4, concentrated water at a concentrated water port of the nanofiltration membrane concentration unit 4 is conveyed to a nanofiltration concentrated water tank 5 for caching, concentrated water cached by the nanofiltration concentrated water tank 5 is conveyed to a freezing recrystallization unit 6, and the received concentrated water of the nanofiltration concentrated water tank 5 is subjected to freezing recrystallization through the freezing recrystallization unit 6;
the water produced at the water producing port of the nanofiltration membrane concentration unit 4 is conveyed to the nanofiltration water producing tank 7 for caching, the water produced cached by the nanofiltration water producing tank 7 is conveyed to the evaporation crystallization unit 8, the evaporation crystallization unit 8 is used for evaporating and crystallizing the received water produced by the nanofiltration water producing tank 7, the evaporation port evaporation liquid of the evaporation crystallization unit 8 is conveyed to the second dilution unit 9 for dilution, and the diluted dilution liquid is conveyed to the selective membrane salt separating unit 10 for monovalent salt.
In this embodiment, the product of the freeze-recrystallization unit 6 is sent to a first drying unit 11, and the received product of the freeze-recrystallization unit 6 is dried by the first drying unit 11 to obtain anhydrous sodium sulfate. The product of the evaporative crystallization unit 8 is fed to a second drying unit 12, and the product of the evaporative crystallization unit 8 received is dried by the second drying unit 12 to obtain sodium chloride. And the concentrated water at the concentrated water port of the selective membrane salt separating unit 10 is returned to the nanofiltration water production tank 7 through a return pipeline. Delivering the produced water at the water producing port of the selective membrane salt separating unit 10 to a salt separating water producing tank 13 for buffering; delivering the produced water buffered by the salt separating and producing water tank 13 to an evaporation and concentration unit 14, and performing evaporation and concentration on the received produced water of the salt separating and producing water tank 13 through the evaporation and concentration unit 14; the concentrated water liquid of the evaporation and concentration unit 14 is conveyed to a cooling unit 15, and the cooling unit 15 cools the received concentrated water liquid of the evaporation and concentration unit 14 to separate out sodium nitrate crystals; the sodium nitrate crystals precipitated by the cooling unit 15 are conveyed to a third drying unit 16, and the sodium nitrate crystals precipitated by the cooling unit 15 are dried by the third drying unit 16. The condensate of the freezing recrystallization unit 6, the evaporation crystallization unit 8 and the evaporation concentration unit 14 is conveyed to a condensate water tank 17 for buffering.
According to the technical scheme, the evaporation mother liquor passes through the hard removal impurity removal unit 1, coagulant aid, softening agent and the like are added to remove certain hardness and suspended matters, the generated sludge can be introduced into a sludge treatment system, and then the evaporation mother liquor after being diluted by the first dilution unit 2 is about 200000-300000 mg/L. The evaporated mother liquor diluted by the first dilution unit 2 enters the nanofiltration membrane concentration unit 4, and the nanofiltration membrane concentration unit 4 can select one-stage or multi-stage concentration according to the water quality condition, so that the main salt components in nanofiltration produced water are monovalent salts. The concentrated solution produced by the nanofiltration membrane concentration unit 4 is mainly bivalent sulfate (Na 2 SO 4 ) At this time Na 2 SO 4 The content of (2) is 15% -20%. Enters a freezing recrystallization unit 6 for recycling. The main components of the produced water produced by the nanofiltration membrane concentration unit 4 are monovalent chloride (NaCl) and nitrate (NaNO) 3 ) In order to realize the resource utilization of monovalent salt, an evaporation crystallization unit 8 and a selective membrane salt separation unit 10 are adopted to treat the part of nanofiltration produced water. The water produced by nanofiltration in the evaporation crystallization unit 8 is mainly sodium chloride solution, the evaporated concentrated solution enters the selective membrane salt separation unit 10 after being diluted by the first dilution unit 2, the selective membrane salt separation unit 10 has extremely high rejection rate to chloride ions and relatively low rejection rate to nitrate ions, so the water produced by the selective membrane salt separation unit 10 is mainly sodium nitrate solution, and the water produced by the selective membrane salt separation unit 10 (NaNO 3 Solution) enters the evaporative concentration unit 14 for concentration. The concentrated water (NaCl solution) of the selective membrane concentration unit flows back to the nanofiltration water production tank 7 to continue the evaporation crystallization. Evaporating the concentrated solution (NaNO) 3 ) The temperature-reducing and cooling unit 15 is used for reducing the temperature and cooling, and sodium nitrate crystals are separated out.
In summary, the invention is provided with a hard removing and impurity removing unit 1, a first diluting unit 2, a filtering unit 3, a nanofiltration membrane concentrating unit 4, a nanofiltration concentrate tank 5, a freezing recrystallization unit 6, a nanofiltration product tank 7, an evaporation crystallization unit 8, a second diluting unit 9 and a selective membrane salt separating unit 10; the hard removing and impurity removing unit 1 is connected with the first diluting unit 2 through a conveying pipeline, and the hard removing and impurity removing unit 1 is used for purifying and preprocessing the received evaporation mother liquor; the first dilution unit 2 is connected with the filtering unit 3 through a conveying pipeline, and the first dilution unit 2 is used for diluting the evaporation mother liquor after the received purification pretreatment of the hard removal and impurity removal unit 1; the filtering unit 3 is connected with the nanofiltration membrane concentration unit 4 through a conveying pipeline, and the filtering unit 3 is used for filtering the evaporation mother liquor diluted by the received first dilution unit 2; the concentrated water port of the nanofiltration membrane concentration unit 4 is connected with a filtration concentrated water tank 5 through a conveying pipeline, and the nanofiltration membrane concentration unit 4 is used for separating monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank 5 is connected with the freezing recrystallization unit 6 through a conveying pipeline, and the nanofiltration concentrated water tank 5 is used for caching the received concentrated water of the nanofiltration membrane concentration unit 4; the freezing and recrystallizing unit 6 is used for freezing and recrystallizing the concentrated water in the received nanofiltration concentrated water tank 5; the water producing port of the nanofiltration membrane concentration unit 4 is connected with a filtration water producing tank 7 through a conveying pipeline, the nanofiltration water producing tank 7 is connected with an evaporation crystallization unit 8 through a conveying pipeline, and the nanofiltration water producing tank 7 is used for caching the water produced by the received nanofiltration membrane concentration unit 4; the evaporation port of the evaporation crystallization unit 8 is connected with a second dilution unit 9 through a conveying pipeline, and the evaporation crystallization unit 8 is used for performing evaporation crystallization on the received water produced by the nanofiltration water production tank 7; the second dilution unit 9 is connected with a selective membrane salt separation unit 10 through a conveying pipeline, the second dilution unit 9 is used for diluting the received concentrated solution of the evaporative crystallization unit 8, and the selective membrane salt separation unit 10 is used for monovalent salt separation of the received diluted solution of the second dilution unit 9. The whole process firstly performs dilution, hard removal and impurity removal, and performs pretreatment work for subsequent salt separation treatment; the method is characterized in that monovalent salt and multivalent salt are separated and concentrated through nanofiltration membrane, nanofiltration concentrated water is mainly divalent salt concentrated solution (TDS 150000 mg/L-160000 mg/L) and is subjected to freezing recrystallization to realize the recycling of divalent salt. The nanofiltration water is mainly monovalent salt (sodium chloride and sodium nitrate), and finally, in order to realize the recycling of the monovalent salt, the sodium chloride is separated according to the different solubility of the monovalent salt; and separating and concentrating the evaporated concentrated solution by using a selective membrane element. The remaining sodium nitrate is separated by evaporating concentration and cooling. The resource utilization of sodium chloride, sodium sulfate and sodium nitrate is truly realized for the evaporation mother liquor. The invention adopts nanofiltration membrane concentration, has the advantages of open fluid channel, wide flowing, excellent self-cleaning effect, reduced pressure loss of vortex rotating flow channels, wider applicability, no need of complex pretreatment, and more stable performance; the separation of the impurity salts (monovalent salt and multivalent salt) in the evaporation mother liquor can be realized; the evaporation mother liquor can be effectively treated, so that the problem of high nitrate concentration is solved; realizes the reclamation of the mixed salt, finishes the process of changing waste into valuable, reduces the treatment cost and truly realizes the economic benefit and the social benefit.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. The evaporation mother liquor treatment system is characterized by comprising a hard removing impurity unit (1), a first dilution unit (2), a filtering unit (3), a nanofiltration membrane concentration unit (4), a nanofiltration concentrate water tank (5), a freezing recrystallization unit (6), a nanofiltration product water tank (7), an evaporation crystallization unit (8), a second dilution unit (9) and a selective membrane salt separation unit (10);
the hard removing and impurity removing unit (1) is connected with the first dilution unit (2) through a conveying pipeline, and the hard removing and impurity removing unit (1) is used for purifying and preprocessing the received evaporation mother liquor;
the first dilution unit (2) is connected with the filtering unit (3) through a conveying pipeline, and the first dilution unit (2) is used for diluting the evaporation mother liquor after the received purification pretreatment of the hard and impurity removal unit (1);
the filtering unit (3) is connected with the nanofiltration membrane concentration unit (4) through a conveying pipeline, and the filtering unit (3) is used for filtering the received evaporation mother liquor diluted by the first dilution unit (2);
the concentrated water port of the nanofiltration membrane concentration unit (4) is connected with the nanofiltration concentrated water tank (5) through a conveying pipeline, and the nanofiltration membrane concentration unit (4) is used for separating monovalent salt from divalent salt from the received evaporation mother liquor; the nanofiltration concentrated water tank (5) is connected with the freezing recrystallization unit (6) through a conveying pipeline, and the nanofiltration concentrated water tank (5) is used for caching the received concentrated water of the nanofiltration membrane concentration unit (4); the freezing and recrystallizing unit (6) is used for freezing and recrystallizing the received concentrated water in the nanofiltration concentrated water tank (5);
the water outlet of the nanofiltration membrane concentration unit (4) is connected with the nanofiltration water production tank (7) through a conveying pipeline, the nanofiltration water production tank (7) is connected with the evaporation crystallization unit (8) through a conveying pipeline, and the nanofiltration water production tank (7) is used for caching the received water produced by the nanofiltration membrane concentration unit (4); the evaporation port of the evaporation crystallization unit (8) is connected with the second dilution unit (9) through a conveying pipeline, and the evaporation crystallization unit (8) is used for performing evaporation crystallization on the received water produced by the nanofiltration water production tank (7); the second dilution unit (9) is connected with the selective membrane salt separation unit (10) through a conveying pipeline, the second dilution unit (9) is used for diluting the received concentrated solution of the evaporative crystallization unit (8), and the selective membrane salt separation unit (10) is used for performing monovalent salt separation on the received diluted solution of the second dilution unit (9);
the device further comprises a first drying unit (11), wherein the freezing and recrystallizing unit (6) is connected with the first drying unit (11) through a conveying pipeline, and the first drying unit (11) is used for drying the received product of the freezing and recrystallizing unit (6) to obtain anhydrous sodium sulfate;
the device further comprises a second drying unit (12), wherein the second drying unit (12) is connected with the evaporative crystallization unit (8) through a conveying pipeline, and the second drying unit (12) is used for drying the received product of the evaporative crystallization unit (8) to obtain sodium chloride;
the water concentration port of the selective membrane salt separation unit (10) is connected with the nanofiltration water production tank (7) through a return pipeline;
the water outlet of the selective membrane salt separation unit (10) is connected with a salt separation water production tank (13) through a conveying pipeline, and the salt separation water production tank (13) is used for caching the received water produced by the selective membrane salt separation unit (10);
the salt separation water production tank (13) is connected with an evaporation concentration unit (14) through a conveying pipeline, and the evaporation concentration unit (14) is used for performing evaporation concentration on the received produced water of the salt separation water production tank (13);
the evaporation and concentration unit (14) is connected with a cooling unit (15) through a conveying pipeline, and the cooling unit (15) is used for cooling the received concentrated water solution of the evaporation and concentration unit (14) so as to separate out sodium nitrate crystals.
2. An evaporation mother liquor treatment system according to claim 1, wherein the cooling unit (15) is connected with a third drying unit (16) through a conveying pipeline, and the third drying unit (16) is used for drying sodium nitrate crystals separated out by the cooling unit (15).
3. An evaporation mother liquor treatment system according to claim 2, further comprising a condensed water tank (17), wherein the freezing recrystallization unit (6), the evaporation crystallization unit (8) and the evaporation concentration unit (14) are connected to the condensed water tank (17) via a conveying pipeline, and the condensed water tank (17) is used for receiving condensate generated by the freezing recrystallization unit (6), the evaporation crystallization unit (8) and the evaporation concentration unit (14).
4. An evaporation mother liquor treatment process employing an evaporation mother liquor treatment system as claimed in any one of claims 1 to 3, comprising the steps of:
the evaporation mother liquor containing sodium nitrate, sodium chloride and sodium sulfate is conveyed to a hard removing and impurity removing unit (1), and the received evaporation mother liquor is subjected to purification pretreatment through the hard removing and impurity removing unit (1);
the evaporation mother liquor after the purification pretreatment of the hard removal and impurity removal unit (1) is conveyed to a first dilution unit (2), and the evaporation mother liquor after the purification pretreatment of the hard removal and impurity removal unit (1) is received is diluted by the first dilution unit (2);
the evaporated mother liquor diluted by the first dilution unit (2) is conveyed to a filtering unit (3), and the received evaporated mother liquor diluted by the first dilution unit (2) is filtered by the filtering unit (3);
delivering the evaporation mother liquor filtered by the filtering unit (3) to a nanofiltration membrane concentration unit (4), separating monovalent salt and divalent salt from the received evaporation mother liquor by the nanofiltration membrane concentration unit (4), delivering concentrated water at a concentrated water port of the nanofiltration membrane concentration unit (4) to a nanofiltration concentrated water tank (5) for caching, delivering the concentrated water cached by the nanofiltration concentrated water tank (5) to a freezing recrystallization unit (6), and freezing and recrystallizing the received concentrated water of the nanofiltration concentrated water tank (5) by the freezing recrystallization unit (6);
delivering water produced at a water producing port of the nanofiltration membrane concentration unit (4) to a nanofiltration water producing tank (7) for caching, delivering the water produced cached by the nanofiltration water producing tank (7) to an evaporation crystallization unit (8), performing evaporation crystallization on the received water produced by the nanofiltration water producing tank (7) through the evaporation crystallization unit (8), delivering evaporation port evaporation liquid of the evaporation crystallization unit (8) to a second dilution unit (9) for dilution, and delivering diluted dilution liquid to a selective membrane salt separating unit (10) for monovalent salt separation.
5. The evaporation mother liquor treatment process according to claim 4, further comprising:
delivering the product of the freeze-recrystallization unit (6) to a first drying unit (11), drying the received product of the freeze-recrystallization unit (6) by the first drying unit (11) to obtain anhydrous sodium sulfate;
delivering the product of the evaporative crystallization unit (8) to a second drying unit (12), drying the received product of the evaporative crystallization unit (8) by the second drying unit (12) to obtain sodium chloride;
the concentrated water at the concentrated water port of the selective membrane salt separating unit (10) is returned to the nanofiltration water production tank (7) through a return pipeline;
delivering the produced water at the water producing port of the selective membrane salt separating unit (10) to a salt separating water producing tank (13) for caching; delivering the produced water buffered by the salt separating and producing water tank (13) to an evaporation and concentration unit (14), and carrying out evaporation and concentration on the received produced water of the salt separating and producing water tank (13) through the evaporation and concentration unit (14);
the concentrated water liquid of the evaporation concentration unit (14) is conveyed to a cooling unit (15), and the cooling unit (15) is used for cooling the received concentrated water liquid of the evaporation concentration unit (14) so as to separate out sodium nitrate crystals;
sodium nitrate crystals precipitated by the cooling unit (15) are conveyed to a third drying unit (16), and the sodium nitrate crystals precipitated by the cooling unit (15) are dried through the third drying unit (16);
and conveying condensate of the freezing recrystallization unit (6), the evaporation crystallization unit (8) and the evaporation concentration unit (14) to a condensate water tank (17) for caching.
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