CN108623104B - High-salinity wastewater zero-emission treatment method and device based on nanofiltration membrane allocation - Google Patents
High-salinity wastewater zero-emission treatment method and device based on nanofiltration membrane allocation Download PDFInfo
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- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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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
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- 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
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- 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
- C01D3/14—Purification
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- 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
- C01D5/16—Purification
-
- 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
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
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- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
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- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/722—Oxidation by peroxides
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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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- 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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- 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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to a high-salt wastewater zero-emission treatment method and device based on a nanofiltration membrane allocation system. The process mainly comprises the following steps: the high-salt wastewater is subjected to impurity removal, salt concentration and softening by a pretreatment system, the softened concentrated water enters a nanofiltration preparation system, the concentration of divalent salt is prepared, the concentration ratio of divalent salt of the nanofiltration concentrated water is between 0.01 and 0.1, the concentrated water enters a sodium sulfate crystallization system to obtain divalent salt products meeting the requirements of industrial salt and mother liquor containing sodium chloride, the permeate of the nanofiltration preparation system enters a sodium chloride crystallization system to obtain sodium chloride products and mother liquor containing sodium sulfate after being subjected to re-concentration, the sodium chloride crystallization mother liquor enters a sodium sulfate crystallization system after being subjected to impurity removal, and the sodium sulfate crystallization mother liquor enters the sodium chloride crystallization system after being subjected to impurity removal, so that the wastewater zero emission is realized and the salt concentration fluctuation in the crystallization system is stabilized.
Description
Technical Field
The application relates to a high-salt wastewater zero-emission treatment method and device based on nanofiltration membrane allocation, and belongs to the technical field of water treatment.
Background
The waste water discharged by paper industry, printing and dyeing industry, chemical industry, pharmaceutical industry and the like contains inorganic salt with a certain concentration, and the process of separating the inorganic salt from the waste water is involved in the zero discharge treatment process of the waste water. The COD and SS are reduced by adopting advanced oxidation pretreatment aiming at zero emission of the salt-containing wastewater, the salt-containing wastewater is concentrated by adopting a reverse osmosis membrane on the basis, and the hardness in the wastewater is gradually increased along with the increase of concentration multiple. The hardness of the concentrated wastewater can be removed by adopting a two-alkali method or a resin softening method. The wastewater subjected to hardness removal is further concentrated through reverse osmosis or electrodialysis and the like, and industrial salt is obtained through an evaporation crystallization process. Clear water generated in the membrane concentration process is used for each production section according to different water qualities. The Chinese patent application (CN 103508602A, CN 104071808A) of the salt-containing wastewater zero discharge technology has been reported, but the problems of how to separate divalent salt are not related in the patents, and the obtained mixed salt is difficult to recycle.
Chinese patent CN105540972a divides the zero-emission process of salt-containing wastewater into three parts, namely cyclic pretreatment, cyclic reduction and zero-emission unit. The separation of salt and nitrate is realized in the process of evaporation crystallization. The process mainly aims at a system with larger concentration difference of monovalent salt and divalent salt in the salt-containing wastewater, industrial grade monovalent salt and divalent salt can be obtained by controlling the operation condition of the crystallization process, and the application range of the patent is limited because the components of the industrial wastewater are complex and the concentration difference of the monovalent salt and the divalent salt is difficult to meet the separation of salt and nitrate.
Chinese patent CN104370405A adopts nanofiltration technology to carry out salt separation treatment on high-concentration brine, and the nanofiltration fresh water is concentrated and then used for softener regeneration. The nanofiltration concentrated water is used for evaporating and crystallizing to obtain a solid substance, and a divalent salt product with high purity can be obtained, but the nanofiltration fresh water is not concentrated to obtain a monovalent salt product, so that the discharge of the part of salt-containing wastewater or the enrichment in a system is caused, and the patent only solves the problem of partial salt utilization.
Disclosure of Invention
The technical problems to be solved by the application are as follows: aiming at the problem that the concentration ratio of sodium chloride and sodium sulfate in the salt-containing wastewater is not suitable for separation by adopting a crystallization method, the concentration of monovalent salt and divalent salt in the salt-containing wastewater is adjusted by adopting a nanofiltration process, so that the wastewater with the nanofiltration membrane subjected to the proportion adjustment can be further concentrated by adopting a reverse osmosis or electrodialysis process, and the concentrated salt-containing wastewater can be respectively subjected to corresponding crystallization processes to obtain sodium chloride and sodium sulfate industrial salt.
The first aspect of the application:
a zero discharge method of high-salt wastewater comprises the following steps:
step 1, removing impurities from salt-containing wastewater by a pretreatment system;
step 2, concentrating the wastewater obtained in the step 1;
step 3, softening the wastewater obtained in the step 2;
step 4, filtering the wastewater obtained in the step 3 by adopting a nanofiltration membrane, and regulating NaCl and Na in the wastewater 2 SO 4 Concentration ratio;
step 5, feeding the concentrated water of the nanofiltration membrane into Na 2 SO 4 Crystallization system, na is obtained through crystallization separation 2 SO 4 Industrial salt and a first mother liquor; concentrating the fresh water with nanofiltration membrane, and feedingIn a NaCl crystallization system, obtaining NaCl industrial salt and a second mother solution through crystallization and separation;
step 6, the first mother liquor is sent into a NaCl crystallization system for crystallization treatment, and the second mother liquor is sent into Na 2 SO 4 The crystallization system performs crystallization treatment.
In one embodiment, the COD of the effluent of the pretreatment system in the step 1 is between 10 and 200mg/L, and the SS is between 3 and 50mg/L.
In one embodiment, the pretreatment in step 1 refers to a combination of one or more of prefiltering, biofiltering, precipitation, oxidation, or ultrafiltration.
In one embodiment, the prefiltering is one or a combination of sand filtration, multi-media filtration, or activated carbon filtration.
In one embodiment, the oxidation employs one or a combination of ozone oxidation, fenton oxidation, or microwave oxidation; the biological filter is an activated carbon biological filter.
In one embodiment, the concentration treatment leads the TDS in the wastewater to be between 20 and 60g/L; the concentration process adopts one or more of nanofiltration membrane concentration, reverse osmosis concentration or electrodialysis concentration.
In one embodiment, the hardness of the effluent of the softening system in the step 3 is between 20 and 200 mg/L; the softening process may employ one or more of membrane softening, agent softening, or ion exchange resin softening.
In one embodiment, in step 4, the nanofiltration membrane concentrates NaCl and Na 2 SO 4 Concentration mass ratio of concentration is 0.01-0.07: 1, a step of; na in concentrated water of nanofiltration membrane 2 SO 4 The mass concentration is 8-15%.
In one embodiment, in step 5, the concentration of the fresh water of the nanofiltration membrane is performed by one or a combination of a plurality of high-pressure reverse osmosis membrane technology, DTRO technology, electrodialysis technology, MVR evaporation technology or multi-effect evaporation technology; the mass concentration of NaCl after the nanofiltration membrane fresh water concentration is between 10 and 20 percent.
In one embodiment, the first mother liquor is concentrated before being fed to NaCl crystallizationCrystallizing in the system, concentrating the second mother liquid, and feeding Na 2 SO 4 The crystallization system performs crystallization treatment.
A second aspect of the application:
a high-salt wastewater zero-emission treatment device, comprising:
the pretreatment system is used for carrying out pretreatment and impurity removal on the high-salt wastewater;
the concentration system is connected with the pretreatment system and is used for concentrating the wastewater obtained by the pretreatment system;
the softening system is connected with the concentrating system and is used for softening the concentrated wastewater;
the nanofiltration membrane is connected with the softening system and is used for separating divalent salt from the softened produced water;
the sodium sulfate crystallization system is connected to the concentrated solution side of the nanofiltration membrane and is used for crystallizing the nanofiltration concentrated solution to obtain Na 2 SO 4 ；
And the sodium chloride crystallization system is connected to the dilute side of the nanofiltration membrane and is used for crystallizing the nanofiltration dilute to obtain NaCl.
In one embodiment, the mother liquor outlet of the sodium sulfate crystallization system is connected to the sodium chloride crystallization system and the mother liquor outlet of the sodium chloride crystallization system is connected to the sodium sulfate crystallization system.
In one embodiment, the pretreatment system comprises one or more of a prefilter, a biofilter, a precipitation device, an oxidation device, or an ultrafiltration device.
In one embodiment, the prefilter device is one or a combination of sand filter devices, multi-media filter devices, or activated carbon filter devices.
In one embodiment, the biofilter unit is an activated carbon biofilter unit.
In one embodiment, the oxidizing device is one or a combination of ozone oxidizing device, fenton oxidizing device, or microwave oxidizing device.
In one embodiment, the concentration system comprises one or more of a nanofiltration membrane concentration device, a reverse osmosis concentration device, or an electrodialysis concentration device.
In one embodiment, the dilute side of the nanofiltration membrane is connected to a sodium chloride crystallization system via a concentrating device.
In one embodiment, the concentrating device is selected from one or a combination of several of a high pressure reverse osmosis membrane device, a DTRO device, an electrodialysis device, an MVR evaporation device or a multiple effect evaporation device.
Advantageous effects
The application has wide adaptability to the salt-containing wastewater, and the proportion of monovalent salt and divalent salt is regulated by controlling the concentration multiple and the retention rate of nanofiltration, thereby meeting the requirements of subsequent NaCl and Na 2 SO 4 The requirements of the respective crystallization recycling process are met, zero emission of wastewater is realized, industrial grade monovalent salt and divalent salt products with high purity are obtained, and the method has the advantages of energy conservation, high efficiency and emission reduction.
The application has the main innovation point that the nanofiltration membrane is used for adjusting the proportion of monovalent salt to divalent salt in the high-salt wastewater, thereby meeting the requirements of NaCl and Na 2 SO 4 And according to the requirement of separate crystallization, mother liquor in the crystallization process is recycled, so that the mother liquor amount is reduced, and the salt utilization efficiency in the salt and nitrate co-production process is improved. Finally, the monovalent salt and the divalent salt with high purity are obtained while realizing zero emission of the salt-containing wastewater, and the recycling utilization of water and inorganic salt is realized.
In addition, due to the presence of NaCl and Na 2 SO 4 In the process of crystallization, naCl and Na in the crystallization liquid 2 SO 4 The larger the concentration ratio difference, the more favorable the crystallization process to form high purity crystalline salts. And because the salt concentration in the high-salt wastewater can periodically fluctuate, the concentration in the dilute solution and the concentrated solution obtained in the nanofiltration process can be easily caused to periodically fluctuate, and the crystallization process is influenced. Therefore, naCl and Na can be effectively caused by adopting a crystallization system which returns to the previous stage after the mother solution after crystallization is further concentrated by adopting a reverse osmosis membrane 2 SO 4 The fluctuation value of the concentration ratio of (c) is reduced, and the occurrence of instability in the crystallization process is suppressed.
Drawings
FIG. 1 is a flow chart of the overall method provided by the present application.
Fig. 2 is a diagram of an apparatus provided by the present application.
Wherein, 1, a pretreatment system; 2. a concentrating system; 3. a softening system; 4. nanofiltration membrane; 5. a sodium sulfate crystallization system; 6. and a sodium chloride crystallization system.
Detailed Description
The present application will be described in further detail with reference to the following specific embodiments. It will be appreciated by those skilled in the art that the following examples are illustrative of the present application and should not be construed as limiting the scope of the application. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Values expressed in a range format are to be understood to include not only the numerical values explicitly recited as the limits of the range, but also all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
Reference in the specification to "one embodiment," "another embodiment," "implementation," etc., means that a particular feature, structure, or inclusion in at least one embodiment described in general in connection with the embodiment is described. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is intended to be within the scope of the application to implement such feature, structure, or characteristic in connection with other embodiments.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or be indirectly connected to the other element with the element interposed therebetween. Unless explicitly stated to the contrary, the terms "comprising" and "having" should be understood to mean inclusion of the listed elements rather than excluding any other element.
The words "comprise," "include," "have" or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The application relates to a process for zero discharge of high-salt wastewater, which mainly comprises NaCl and Na 2 SO 4 Waste water containing substances such as COD and the like, and also contains a part of Ca 2+ 、Mg 2+ Hardness of the steel sheet, etc. The high-salt wastewater mainly can be derived from reclaimed water and tail water after treatment in the papermaking process, or can be reclaimed water and tail water obtained by treatment of wastewater in coal chemical industry, and the like. Some typical water quality conditions are: COD is 10-200 mg/L, and the total hardness is 50-1000 mg/L (CaCO is used) 3 Meter), TDS is 1000-20000 mg/L, total suspended substance SS is 3-50 mg/L, naCl concentration is 200-5000 mg/L, na 2 SO 4 The concentration range of (2) is 200-5000 mg/L. The process of the application is particularly suitable for NaCl and Na 2 SO 4 The concentration ratio of (2) cannot be directly separated by evaporation crystallization; for example NaCl and Na 2 SO 4 The mass concentration ratio of (2) is 10:1 to 1:10, may be 5:1 to 1:5, may be 2:1 to 1:2.
the main process flow is as follows:
step 1: removing impurities from the high-salt wastewater by a pretreatment system, and discharging water from the pretreatment system;
step 2: removing impurities, then, entering a salt concentration system, enabling TDS in wastewater to be 20-60 g/L, and enabling reverse osmosis fresh water to enter a reuse water system;
step 3, enabling concentrated water of the salt concentration system to enter a softening system, wherein the hardness of water discharged from the softening system is 50-200 mg/L;
step 4, the softened concentrated water enters a nanofiltration blending system to blend the concentration of divalent salt, so that the concentration ratio of divalent salt of the nanofiltration concentrated water is between 0.01 and 0.1;
step 5, the concentrated water of the nanofiltration blending system enters Na 2 SO 4 The crystallization system obtains Na meeting the industrial salt requirement 2 SO 4 Industrial salts and mother liquor;
step 6, allowing the permeate of the nanofiltration blending system to enter a NaCl crystallization system after passing through a re-concentration system to obtain NaCl industrial salt and mother liquor;
step 7, na 2 SO 4 Condensed water of the crystallization system and the NaCl crystallization system enters a reuse water system Na 2 SO 4 The mother liquor discharged from the crystallization system enters the NaCl crystallization system after impurity removal, and the mother liquor discharged from the NaCl crystallization system enters Na after impurity removal 2 SO 4 In the crystallization system, zero discharge of wastewater is realized;
and 8, after the purified water of each system is prepared by a reuse water system, different reuse requirements are met, and the quality-divided water supply is realized.
Furthermore, the pretreatment unit in step 1 mainly adopts conventional processes of pre-removing impurities from water, and aims to remove impurities which are easier to remove in the wastewater, reduce loads of a subsequent membrane process, an evaporation process and the like, and improve water quality, wherein the pretreatment can be performed according to conventional treatment steps, and can comprise one or more of pre-filtration, precipitation and oxidation processes. Among them, the prefilter is generally exemplified by a centrifugal separation system, a press separation system, a filtration system, a floating separation system, and a sedimentation separation system. Examples of the centrifugal separation method include a horizontal continuous centrifuge (spiral decanter process), a separation plate centrifuge, a centrifugal filter, and a mansion pules type ultracentrifuge, examples of the filtration method include a belt filter, a belt press, a screw press, a precoat filter, and a filter press, examples of the floating separation method include a continuous floating separation device, examples of the sedimentation separation method include an aggregation sedimentation separation method, and examples of the sedimentation separation method include a continuous floating separation device, and examples of the sedimentation separation method include a sedimentation separation methodThe machine, the rapid sedimentation separator, etc., but are not particularly limited to any of the above. However, the membrane loading upon microfiltration and/or ultrafiltration membrane treatment can be reduced by any one or a combination of the above. Particularly preferably, the pretreatment process may employ one or more of sand filtration, multi-media filtration, activated carbon filtration. The biological filter process refers to removing macromolecules or other impurities in water by using an adsorption material with high specific surface area as a carrier, wherein the carrier can be a conventional organic or inorganic adsorption material, for example: adsorption materials such as macroporous adsorption resin, zeolite, active carbon and the like; the biological activated carbon filter adopts a downward flow type, the content of the dissolved oxygen in the inflow water is generally about 5-10 mg/L, and the requirement of biodegradation on the dissolved oxygen can be fully ensured; the filter tank can adopt two-section air-water back flushing, namely, air scrubbing is firstly carried out, then sand filtering water back flushing without chlorine is carried out, and the back flushing period is 1-10 days; when activated carbon is used as a carrier for filling the biological filter, the standard for evaluating the activated carbon is generally adopted for iodine value and methylene blue adsorption value, the adsorption quantity can be 300-2000 mg/g and 50-500 mg/g respectively, and the stacking density of the activated carbon can be 50-600 g/L. The sedimentation refers to a method for separating particle impurities from wastewater by gravity sedimentation or sedimentation under the action of other external forces, and can be a sedimentation tank and the like; the oxidation is a method for purifying the wastewater by oxidizing and decomposing pollutants in the wastewater by using an oxidant, and when advanced oxidation treatment is adopted, the method mainly comprises a Fenton oxidation method, an ozone combined oxidation method, a wet oxidation method, a supercritical water oxidation method, a photocatalytic oxidation method, an ultrasonic oxidation method and the like, and particularly, one or more of an ozone oxidation technology, a Fenton technology and a microwave oxidation are preferably adopted for combined treatment. When ozone oxidation is adopted, the ozone concentration can be 10-500 ppm, and the oxidation temperature can be 10-50 ℃; when Fenton oxidation is adopted, fe 2+ And H 2 O 2 The concentration can be respectively 10-50 mg/L and 20-900 mg/L, the pH value of the system is 3-6, the reaction temperature is 10-60 ℃, and the reaction time is 10-240 min; when microwave oxidation is adopted, the frequency is 400-3000 MHz, the oxidation temperature is 10-60 ℃, and the treatment time is 20-200 min. Pretreatment ofThe ultrafiltration used in the present specification refers to a process of filtering colloidal and macromolecular impurities in water by an ultrafiltration membrane, and in the present specification, "ultrafiltration membrane" refers to a filtration membrane having a pore size of 0.001 to 0.01 μm and/or a filtration membrane having a molecular weight cut-off of about 1000 to 300000, and the ultrafiltration membrane may be further classified into hydrophobic and hydrophilic by using an inorganic membrane and an organic membrane. Examples of the hydrophobic organic film include, but are not limited to, polysulfone, polyethersulfone, polyether, polyvinylidene fluoride, polyethylene, polypropylene, and the like. The hydrophilic organic film is not limited to this, and examples thereof include polyacrylonitrile, polyamide, polyimide, cellulose acetate, and the like. The filter element comprises flat membrane, tubular membrane, spiral membrane, hollow fiber (hollow fiber) membrane, etc.
Further, in the salt concentration system in step 2, the concentration multiple is 2-20 times, a proper concentration multiple is selected according to the salt concentration of the inlet water, and after concentration, the salt concentration of 10-40 g/L is the preferable salt concentration, but can be properly adjusted according to the difference of salt components in the inlet water and the change of the salt concentration of the inlet water, and the concentration is not the determining condition of the process implementation. The salt concentration system in the step 2 adopts one or a plurality of process combinations of nanofiltration membrane concentration, reverse osmosis concentration and electrodialysis concentration.
The nanofiltration membrane according to the present application is defined as a membrane "pressure-driven membrane for preventing particles smaller than 2nm and dissolved macromolecules", and polymer materials such as cellulose acetate polymers, polyamides, sulfonated polysulfones, polyacrylonitrile, polyesters, polyimides, and vinyl polymers can be used. The reverse osmosis membrane of the present application may be made of a polymer material such as cellulose acetate polymer, polyamide, polyester, polyimide, or vinyl polymer. The operating pressure of the nanofiltration membrane can be controlled to be 0.5-4.0 MPa, and the operating pressure of the reverse osmosis membrane can be controlled to be 1.0-10 MPa.
Further, the softening process in the step 3 aims to remove Ca in the wastewater 2+ 、Mg 2+ The ions can be softened by membrane and agent (such as NaOH and Na 2 CO 3 ) And softening the ion exchange resin.
Further toIn general, naCl and Na in reclaimed water 2 SO 4 The concentration ratio of (2) is not satisfactory for obtaining NaCl and Na by crystallization 2 SO 4 When the requirements of the application are met, the nanofiltration membrane is used for adjusting the proportion of monovalent salt and divalent salt in the high-salt wastewater, thereby meeting the requirements of NaCl and Na 2 SO 4 And according to the requirement of separate crystallization, mother liquor in the crystallization process is recycled, so that the mother liquor amount is reduced, and the salt utilization efficiency in the salt and nitrate co-production process is improved. Finally, the monovalent salt and the divalent salt with high purity are obtained while realizing zero emission of the salt-containing wastewater, and the recycling utilization of water and inorganic salt is realized. Nafiiltration of NaCl and Na in concentrated water in step 4 2 SO 4 The mass concentration ratio of (2) is 0.01-0.07.
Furthermore, the re-concentration system in the step 6 adopts a high-pressure reverse osmosis membrane process, a DTRO process and an electrodialysis process, and also can adopt an MVR evaporation process or a multi-effect evaporation process.
Further, the mass concentration of NaCl after the nanofiltration fresh water in the step 4 is concentrated is between 10 and 20 percent.
Further, the nanofiltration concentrated water in the step 4 is concentrated to obtain Na 2 SO 4 The mass concentration is between 8 and 15 percent.
Further, the NaCl crystallization system as described in the 5 th step and the Na as described in the 6 th step 2 SO 4 The evaporation and crystallization process adopted by the crystallization system is one of multi-effect evaporation or MVR evaporation.
Further, the impurity removal process in the step 7 adopts one or more combination processes of ozone oxidation, wet oxidation or micro-electrolysis oxidation.
Furthermore, the reuse water system in the step 8 can realize quality-divided water supply according to the water quality of the produced water of each system, and is used for one or more of front end of boiler makeup water, production water, plant domestic miscellaneous water, circulating water and landscape water.
Further, na 2 SO 4 Concentrating mother liquor of crystallization system, then feeding into NaCl crystallization system for crystallization treatment, concentrating mother liquor of NaCl crystallization system, then feeding into Na 2 SO 4 The crystallization system performs crystallization treatment. Due to monovalent and divalent salts in the wastewaterThe concentration of the salt in water can continuously fluctuate, and the subsequent nanofiltration and crystallization processes can be influenced, so that the process parameters need to be continuously adjusted to adapt to the change of the salt concentration in water, thereby leading to unstable operation process and incapability of meeting the requirement of the purity of the crystallized salt. At the same time, in NaCl and Na 2 SO 4 In the process of crystallization, naCl and Na in the crystallization liquid 2 SO 4 The larger the concentration ratio difference, the more favorable the crystallization process to form high purity crystalline salts. For example: in the process of crystallizing NaCl, naCl and Na in the crystallization liquid 2 SO 4 The concentration ratio of (C) 1 (NaCl)/C 1 (Na 2 SO 4 ) When Na is used 2 SO 4 Mother liquor (concentration is C) containing mainly NaCl obtained after crystallization 2 (NaCl), and C 2 (NaCl)> C 1 (NaCl)) is further concentrated and then added into NaCl for crystallization, so that the concentration of molecules with the ratio can be increased, and the concentration ratio is improved; as can be seen from numerical calculations, when 10 < C 1 (NaCl)/C 1 (Na 2 SO 4 ) When the fluctuation is less than 100, the fluctuation range of the whole ratio can be obviously reduced by increasing the molecular concentration, and the effect of stabilizing the fluctuation is achieved. Na of the same theory 2 SO 4 In the crystallization process of (2), the concentration ratio of a divalent salt is C 1 (Na 2 SO 4 )/C 1 (NaCl) when NaCl is crystallized, the resulting mixture contains mainly Na 2 SO 4 After concentrating the mother liquor of (C) 2 (Na 2 SO 4 ) The concentrated solution returns to Na 2 SO 4 After the crystallization process due to C 2 (Na 2 SO 4 )> C 1 (Na 2 SO 4 ) And the function of stabilizing concentration fluctuation in the crystallization process is also played in the same way. Therefore, naCl and Na can be effectively caused by adopting a crystallization system which returns to the previous stage after the mother solution after crystallization is further concentrated by adopting a reverse osmosis membrane 2 SO 4 The fluctuation value of the concentration ratio of (c) is reduced, and the occurrence of instability in the crystallization process is suppressed.
Based on the above method, the processing device provided by the present application, as shown in fig. 2, includes:
the pretreatment system 1 is used for carrying out pretreatment and impurity removal on the high-salt wastewater;
the concentration system 2 is connected with the pretreatment system 1 and is used for concentrating the wastewater obtained by the pretreatment system 1;
the softening system 3 is connected with the concentrating system 2 and is used for softening the concentrated wastewater;
the nanofiltration membrane 4 is connected with the softening system 3 and is used for separating divalent salt from the softened produced water;
the sodium sulfate crystallization system 5 is connected to the concentrated solution side of the nanofiltration membrane 4 and is used for crystallizing the nanofiltration concentrated solution to obtain Na 2 SO 4 ；
And the sodium chloride crystallization system 6 is connected to the dilute side of the nanofiltration membrane 4 and is used for crystallizing the nanofiltration dilute to obtain NaCl.
In one embodiment, the mother liquor outlet of sodium sulfate crystallization system 5 is connected to sodium chloride crystallization system 6, and the mother liquor outlet of sodium chloride crystallization system 6 is connected to sodium sulfate crystallization system 5.
In one embodiment, the pretreatment system 1 comprises one or more of a prefilter, a biofilter, an oxidizer, a precipitator, an oxidizer, or an ultrafiltration device.
In one embodiment, the prefilter device is one or a combination of sand filter devices, multi-media filter devices, or activated carbon filter devices.
In one embodiment, the combined biofilter, in which the oxidizing device is one or more of an ozone oxidizing device, a Fenton oxidizing device, or a microwave oxidizing device, refers to an activated carbon biofilter device.
In one embodiment, the concentration system 2 includes one or more of a nanofiltration membrane concentration device, a reverse osmosis concentration device, or an electrodialysis concentration device.
In one embodiment, the dilute side of nanofiltration membrane 4 is connected to a sodium chloride crystallization system by a concentrating device.
In one embodiment, the concentrating device is selected from one or a combination of several of a high pressure reverse osmosis membrane device, a DTRO device, an electrodialysis device, an MVR evaporation device or a multiple effect evaporation device.
Example 1
Aiming at a certain pulping wastewater, the nanofiltration and crystallization co-production process is adopted to realize zero wastewater discharge and industrial salt recycling. The daily treatment capacity of raw water of pulping wastewater is 40000 tons. The main water quality parameters are shown in the following table:
the raw water of pulping wastewater is pretreated by sand filtration and an ozone and activated carbon biological filter process after being homogenized in a homogenizing pool, the ozone concentration is 150ppm, and the ozone oxidation time is 40min; hydraulic retention time 15min; the height of the activated carbon biological filter bed is 2.0m, the treatment temperature is 25-30 ℃, and the empty bed contact time is 20min; after pretreatment, the SS of the wastewater is reduced to 12-18 mg/L, the COD concentration is reduced to 45-53 mg/L, and the recovery rate of the pretreated water is more than 97%.
The pretreated salt-containing wastewater enters an ultrafiltration system, the interception molecular weight of an ultrafiltration membrane is 100kDa, the ultrafiltration working pressure is 0.3MPa, and the ultrafiltration operation flux is 50L/(m) 2 H) the ultrafiltration membrane cleaning period exceeds 90 days, the ultrafiltration produced water SDI is less than 2.5, the turbidity is less than 0.2NTU, and the ultrafiltration system recovery rate is more than 93%.
The ultrafiltration water enters a first-stage reverse osmosis system, the reverse osmosis working pressure is 1.5MPa, the temperature is 30 ℃, the reverse osmosis recovery rate is 65%, and the average flux is 15L/(m) 2 H) the TDS of the produced water is lower than 105mg/L. Daily water yield of 24500m 3 . The first-stage reverse osmosis concentrated water enters a weak acid ion exchange resin bed softening system, the hardness of the wastewater is reduced to 170-187 mg/L at 1200-1430 mg/L after passing through the softening system, and the hardness of the wastewater is reduced to 26mg/L after passing through a weak acid cation bed, so that the requirement of the back-stage reverse osmosis is met.
The softened reverse osmosis concentrated water enters a two-stage reverse osmosis system, the reverse osmosis working pressure is 2.0MPa, the temperature is 30 ℃, the TDS of the inlet water is 10250-10560 mg/L, the COD is 187-202 mg/L, the concentration of sodium chloride is 3520-3640 mg/L, and the concentration of sodium sulfate is 63006550mg/L, daily throughput of 13500m 3 . The water recovery rate is 75 percent, and the fresh water yield is 10120m 3 /d, concentrated water volume 3380m 3 And/d. The TDS of the produced water is lower than 210mg/L, the TDS of the concentrated water is 40750-41300 mg/L, the concentration of sodium chloride in the concentrated water is 13450-13920 mg/L, the concentration of sodium sulfate is 24700-25530 mg/L, and the hardness is 392-434 mg/L. The hardness of the concentrated water is reduced to 4-6 mg/L after the concentrated water is softened again by the weak acid cation bed.
The second-stage reverse osmosis concentrated water is subjected to inorganic salt proportion adjustment through a nanofiltration membrane, the operating pressure is 54bar, and the fresh water amount is 2910m after nanofiltration treatment 3 And/d, the concentration of sodium chloride is 14700-15340 mg/L, and the concentration of sodium sulfate in fresh water is 260-285 mg/L. After the nanofiltration fresh water is further concentrated by adopting a high-pressure reverse osmosis and homogeneous membrane electrodialysis technology, the concentration liquid amount is 245m 3 And/d, the concentration of sodium chloride is 191100 ～ 203700mg/L, and the concentration of sodium sulfate is 5380-5500 mg/L. Nanofiltration concentrated water quantity is 480m 3 And/d, the concentration of sodium chloride is 11320-11890 mg/L, and the concentration of sodium sulfate is 174200-17950 mg/L.
Concentrating the nanofiltration fresh water by a reverse osmosis membrane, wherein the NaCl concentration is 31100-31880 mg/L, and the NaCl and Na are 2 SO 4 The mass concentration ratio of (2) is about 53:1, and meets the production requirement of entering the NaCl crystallization process section. The sodium chloride crystallization system adopts three-effect evaporation, adopts the operation mode of advection feeding, salt discharge per effect and mother liquor reflux, controls the crystallization temperature between 40 ℃ and 50 ℃, and crystallizes Na in the mother liquor 2 SO 4 5380mg/L, and sending to a sodium sulfate crystallization system for recycling, and obtaining 45.7 tons of sodium chloride daily. The nanofiltration concentrated water enters a sodium sulfate crystallization system, and the sodium sulfate crystallization system adopts an MVR process to carry out Na 2 SO 4 Crystallizing, controlling the crystallization temperature between 90-105 ℃, na 2 SO 4 And NaCl in a mass concentration ratio of about 13:1, satisfies Na entering 2 SO 4 The crystallization process requires that the mass concentration of NaCl in the crystallization mother liquor is 58400mg/L, and the NaCl is sent to a sodium chloride crystallization system for recycling, and the daily production of the process is 82.5 tons of anhydrous sodium sulfate. The purity of sodium chloride in the two processes reaches 98.3%, and the purity of sodium sulfate reaches 99.0%.
The nanofiltration membrane technology is adopted to regulate the concentration of sodium chloride and sodium sulfate in the salt-containing wastewater, the proportion of fresh water, concentrated water sodium chloride and sodium sulfate meets the requirements of sodium sulfate or sodium chloride co-production technology, the zero emission of the wastewater is finally realized, and the sodium chloride and sodium sulfate which can be recycled are obtained from the wastewater.
Example 2
One existing sewage treatment station of a certain coal chemical industry enterprise has the wastewater discharge amount of 2750m 3 And/h, the wastewater can meet the discharge standard. The quality index of the discharged water is as follows:
the inorganic salt components in the wastewater are mainly sodium chloride and sodium sulfate. And zero discharge treatment is carried out on the wastewater by adopting a nanofiltration and crystallization co-production process.
The coal chemical wastewater is conveyed from a factory to zero-emission raw water, and is subjected to homogenization in a homogenizing pool, and then the raw water is pretreated by adopting sand filtration and ozone and activated carbon adsorption processes, wherein the ozone concentration is 200ppm, and the ozone oxidation time is 50min; activated carbon adsorption temperature is 20 ℃, and hydraulic retention time is 12min; after pretreatment, the SS of the wastewater is reduced to 5-9 mg/L, the COD concentration is reduced to 20-31 mg/L, and the recovery rate of the pretreated water is more than 98%.
The pretreated salt-containing wastewater enters an ultrafiltration system, the interception molecular weight of an ultrafiltration membrane is 50kDa, the ultrafiltration working pressure is 0.4MPa, and the ultrafiltration operation flux is 45L/(m) 2 H) the ultrafiltration membrane cleaning period exceeds 60 days, the ultrafiltration produced water SDI is less than 2, the turbidity is less than 0.3NTU, and the recovery rate of the ultrafiltration system is more than 92%.
The ultrafiltration water enters a first-stage reverse osmosis system, the reverse osmosis working pressure is 2.0MPa, the reverse osmosis recovery rate is 60 percent, and the average flux is 15L/(m) 2 H) the TDS of the produced water is lower than 50mg/L, and the water yield is 1625m 3 And/h. The first-stage reverse osmosis concentrated water enters a weak acid ion exchange resin bed softening system, the hardness of the wastewater is reduced by 30-42 mg/L at 1050-1250 mg/L after passing through the softening system, and the hardness of the wastewater is reduced to below 4mg/L after passing through a weak acid cation bed, so that the requirement of the back-stage reverse osmosis is met.
The softened reverse osmosis concentrated water enters a two-stage reverse osmosis system, the reverse osmosis working pressure is 1.5MPa, the inflow TDS is 4700-5230 mg/L,COD is 38-47 mg/L, sodium chloride concentration is 735-920 mg/L, sodium sulfate concentration is 3860-4340 mg/L, and treatment capacity is 1150m 3 And/h. The water recovery rate is 75 percent, and the fresh water yield is 860m 3 /h, the concentrated water content is 290m 3 And/h. The TDS of the produced water is lower than 100mg/L, the TDS of the concentrated water is 18500-20560 mg/L, the concentration of sodium chloride in the concentrated water is 2900-3130 mg/L, the concentration of sodium sulfate is 15460-17240 mg/L, and the hardness is 76-85 mg/L.
The second-stage reverse osmosis concentrated water enters a third-stage reverse osmosis system, the TDS of the inflow water is 18500-19840 mg/L, the COD is 150-167 mg/L, the concentration of sodium chloride is 2900-3170 mg/L, the concentration of sodium sulfate is 15460-16710 mg/L, and the treatment capacity is 290m 3 And/h. The water recovery rate is 60 percent, and the fresh water yield is 175m 3 /h, concentrated water content 115m 3 And/h. The TDS of the produced water is lower than 400mg/L, the TDS of the concentrated water is 46250-48220 mg/L, the concentration of sodium chloride in the concentrated water is 7050-7280 mg/L, the concentration of sodium sulfate is 38600-40530 mg/L, and the hardness is 76-87 mg/L.
Inorganic salt proportion is prepared from three-stage reverse osmosis concentrated water through nanofiltration membrane, the operating pressure is 48bar, and the fresh water amount is 77m after nanofiltration treatment 3 And/h, the concentration of sodium chloride is 7120-7330 mg/L, and the concentration of fresh water sodium sulfate is 390-419 mg/L. The nanofiltration fresh water is further concentrated by adopting a high-pressure reverse osmosis and homogeneous membrane electrodialysis technology, and the concentration liquid amount is 5.1m 3 And/h, the concentration of sodium chloride is 106080 ～ 113500mg/L, and the concentration of sodium sulfate is 5840-6010 mg/L. Nanofiltration concentrate of 38m 3 And/h, the concentration of sodium chloride is 7035-7230 mg/L, and the concentration of sodium sulfate is 115800 ～ 123400mg/L.
Concentrating nanofiltration fresh water by reverse osmosis membrane, and concentrating NaCl and Na 2 SO 4 The mass concentration ratio of (2) is about 18:1, and meets the production requirement of entering a sodium chloride crystallization system. The sodium chloride crystallization system adopts three-effect evaporation, adopts the operation mode of advection feeding, salt discharge per effect and mother liquor reflux, controls the crystallization temperature between 40 ℃ and 50 ℃, and crystallizes Na in the mother liquor 2 SO 4 The sodium chloride with the mass concentration of 3070mg/L is sent to a sodium sulfate crystallization system for recycling, and 12.7 tons of sodium chloride is obtained daily. The nanofiltration concentrated water enters a sodium sulfate crystallization system, the sodium sulfate crystallization system adopts an MVR process, the crystallization temperature is controlled between 90 ℃ and 105 ℃, and Na is adopted 2 SO 4 And NaCl in a mass concentration ratio of about 16:1, meets the following requirementsEntering the technological requirements of sodium chloride and sodium sulfate, and sending the sodium chloride crystallization system to recycle, wherein the mass concentration of NaCl in the crystallization mother liquor is 33120mg/L, and the daily production of the anhydrous sodium sulfate is 102.6 tons. The purity of sodium chloride in the two processes reaches 98.4%, and the purity of sodium sulfate reaches 99.3%.
The nanofiltration membrane technology is adopted to regulate the concentration of sodium chloride and sodium sulfate in the wastewater in the coal chemical industry, the proportion of fresh water, concentrated water sodium chloride and sodium sulfate meets the requirements of sodium chloride and sodium sulfate crystallization technology, the zero emission of the wastewater is finally realized, and the industrial sodium chloride and sodium sulfate are obtained from the wastewater.
Example 3
Aiming at a certain pulping wastewater, the nanofiltration and crystallization co-production process is adopted to realize zero wastewater discharge and industrial salt recycling. The daily treatment capacity of raw water of pulping wastewater is 40000 tons. The main water quality parameters are shown in the following table:
the raw water of pulping wastewater is pretreated by sand filtration and an ozone and activated carbon biological filter process after being homogenized in a homogenizing pool, the ozone concentration is 150ppm, and the ozone oxidation time is 40min; hydraulic retention time 15min; the height of the activated carbon biological filter bed is 2.0m, the treatment temperature is 25-30 ℃, and the empty bed contact time is 20min; after pretreatment, the SS of the wastewater is reduced to 12-18 mg/L, the COD concentration is reduced to 45-53 mg/L, and the recovery rate of the pretreated water is more than 97%.
The pretreated salt-containing wastewater enters an ultrafiltration system, the interception molecular weight of an ultrafiltration membrane is 100kDa, the ultrafiltration working pressure is 0.3MPa, and the ultrafiltration operation flux is 50L/(m) 2 H) the ultrafiltration membrane cleaning period exceeds 90 days, the ultrafiltration produced water SDI is less than 2.5, the turbidity is less than 0.2NTU, and the ultrafiltration system recovery rate is more than 93%.
The ultrafiltration water enters a first-stage reverse osmosis system, the reverse osmosis working pressure is 1.5MPa, the temperature is 30 ℃, the reverse osmosis recovery rate is 65%, and the average flux is 15L/(m) 2 H) the TDS of the produced water is lower than 105mg/L. Daily water yield of 24500m 3 . The first-stage reverse osmosis concentrated water enters a weak acid ion exchange resin bedThe hardness of the wastewater after passing through the softening system is reduced to 170-187 mg/L at 1200-1430 mg/L, and the hardness of the wastewater after passing through the weak acid cation bed is reduced to 26mg/L, so that the requirement of the reverse osmosis at the rear stage is met.
The softened reverse osmosis concentrated water enters a two-stage reverse osmosis system, the reverse osmosis working pressure is 2.0MPa, the temperature is 30 ℃, the TDS of the inflow water is 10250-10560 mg/L, the COD is 187-202 mg/L, the concentration of sodium chloride is 3520-3640 mg/L, the concentration of sodium sulfate is 6300-6550 mg/L, and the daily treatment capacity is 13500m 3 . The water recovery rate is 75 percent, and the fresh water yield is 10120m 3 /d, concentrated water volume 3380m 3 And/d. The TDS of the produced water is lower than 210mg/L, the TDS of the concentrated water is 40750-41300 mg/L, the concentration of sodium chloride in the concentrated water is 13450-13920 mg/L, the concentration of sodium sulfate is 24700-25530 mg/L, and the hardness is 392-434 mg/L. The hardness of the concentrated water is reduced to 4-6 mg/L after the concentrated water is softened again by the weak acid cation bed.
The second-stage reverse osmosis concentrated water is subjected to inorganic salt proportion adjustment through a nanofiltration membrane, the operating pressure is 54bar, and the fresh water amount is 2910m after nanofiltration treatment 3 And/d, the concentration of sodium chloride is 14700-15340 mg/L, and the concentration of sodium sulfate in fresh water is 260-285 mg/L. After the nanofiltration fresh water is further concentrated by adopting a high-pressure reverse osmosis and homogeneous membrane electrodialysis technology, the concentration liquid amount is 245m 3 And/d, the concentration of sodium chloride is 191100 ～ 203700mg/L, and the concentration of sodium sulfate is 5380-5500 mg/L. Nanofiltration concentrated water quantity is 480m 3 And/d, the concentration of sodium chloride is 11320-11890 mg/L, and the concentration of sodium sulfate is 174200-17950 mg/L.
Concentrating the nanofiltration fresh water by a reverse osmosis membrane, wherein the NaCl concentration is 31100-31880 mg/L, and the NaCl and Na are 2 SO 4 The mass concentration ratio of (2) is about 53:1, and meets the production requirement of entering the NaCl crystallization process section. The sodium chloride crystallization system adopts three-effect evaporation, adopts the operation mode of advection feeding, salt discharge per effect and mother liquor reflux, controls the crystallization temperature between 40 ℃ and 50 ℃, and the crystallization mother liquor is concentrated by high-pressure reverse osmosis to obtain Na 2 SO 4 The mixture with the mass concentration of 217710mg/L is sent to a sodium sulfate crystallization system for recycling, and 48.6 tons of sodium chloride is obtained daily. The nanofiltration concentrated water enters a sodium sulfate crystallization system, and the sodium sulfate crystallization system adopts an MVR process to carry out Na 2 SO 4 Crystallizing, controlling the crystallization temperature between 90-105 ℃, na 2 SO 4 And NaCl mass concentrationThe degree ratio is about 13:1, and satisfies the requirement of entering Na 2 SO 4 The crystallization process requires that the crystallization mother liquor is subjected to high-pressure reverse osmosis concentration, and then the mass concentration of the medium NaCl is 63320mg/L, and the medium NaCl is sent to a sodium chloride crystallization system for recycling, and the daily production of the process is 84.7 tons of anhydrous sodium sulfate. The purity of sodium chloride in the two processes reaches 99.0%, and the purity of sodium sulfate reaches 99.4%.
The nanofiltration membrane technology is adopted to regulate the concentration of sodium chloride and sodium sulfate in the salt-containing wastewater, the proportion of fresh water, concentrated water sodium chloride and sodium sulfate meets the requirements of sodium sulfate or sodium chloride co-production technology, the zero emission of the wastewater is finally realized, and the sodium chloride and sodium sulfate which can be recycled are obtained from the wastewater.
Claims (5)
1. The zero discharge method of the high-salt wastewater is characterized by comprising the following steps of:
step 1, removing impurities from salt-containing wastewater by a pretreatment system; step 1, the COD of the effluent of the pretreatment system is between 10 and 200mg/L, and the SS is between 3 and 50mg/L; the pretreatment in the step 1 refers to one or a combination of a plurality of prefiltering, a biological filter, precipitation, oxidation or ultrafiltration;
step 2, concentrating the wastewater obtained in the step 1; concentrating to make TDS in the wastewater be 20-60 g/L;
step 3, softening the wastewater obtained in the step 2; the hardness of the softened water is between 20 and 200 mg/L;
step 4, filtering the wastewater obtained in the step 3 by adopting a nanofiltration membrane, and regulating NaCl and Na in the wastewater 2 SO 4 Concentration ratio; naCl and Na in nanofiltration membrane concentrated water 2 SO 4 Concentration mass ratio of concentration (0.01-0.07): 1, a step of;
step 5, the concentration of sodium chloride in the concentrated water of the nanofiltration membrane is 11320-11890 mg/L, the concentration of sodium sulfate is 174200-17950 mg/L,
feeding Na into 2 SO 4 Crystallization system, na is obtained through crystallization separation 2 SO 4 Industrial salt and a first mother liquor; concentrating nanofiltration fresh water by a reverse osmosis membrane, sending the concentrated nanofiltration fresh water into a NaCl crystallization system, and obtaining NaCl industrial salt through crystallization separation, wherein the NaCl concentration is 31100-31880 mg/LA second mother liquor;
step 6, the first mother liquor is sent into a NaCl crystallization system for crystallization treatment, and the second mother liquor is sent into Na 2 SO 4 The crystallization system carries out crystallization treatment, sodium sulfate crystallization mother liquor is concentrated and then is sent into the NaCl crystallization system for crystallization treatment, and sodium chloride mother liquor is sent into Na after being over-concentrated 2 SO 4 The crystallization system performs crystallization treatment.
2. The high salt wastewater zero release method of claim 1, wherein the prefiltering is one or a combination of sand filtration, multi-media filtration, or activated carbon filtration; the biological filter is an activated carbon biological filter; the oxidation may be one or a combination of ozone oxidation, fenton oxidation, or microwave oxidation.
3. The method for zero discharge of high-salt wastewater according to claim 1, wherein the concentration process adopts one or more of nanofiltration membrane concentration, reverse osmosis concentration or electrodialysis concentration.
4. The method of claim 1, wherein the softening process is one or more of membrane softening, chemical softening, or ion exchange resin softening.
5. The method for zero emission of high-salt wastewater according to claim 1, wherein the Na in the concentrated water of the nanofiltration membrane 2 SO 4 The mass concentration is 8-15%; in the step 5, the fresh water of the nanofiltration membrane is concentrated by adopting one or a combination of a plurality of high-pressure reverse osmosis membrane technology, DTRO technology, electrodialysis technology, MVR evaporation technology or multi-effect evaporation technology; the mass concentration of NaCl after the nanofiltration membrane fresh water concentration is between 10 and 20 percent.
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