CN112390446A - Zero-discharge treatment method for coking wastewater - Google Patents
Zero-discharge treatment method for coking wastewater Download PDFInfo
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
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Images
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
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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
- C02F1/02—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
- C02F1/42—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
- 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
- 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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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C02F2101/10—Inorganic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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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
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- Y02A20/124—Water desalination
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- Life Sciences & Earth Sciences (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention provides a zero discharge treatment method of coking wastewater, which comprises the following steps: pretreating the coking wastewater, wherein the pretreatment comprises flocculation treatment, ultrafiltration treatment and softened water treatment; carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration produced water and primary nanofiltration concentrated water; carrying out secondary nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and tertiary nanofiltration treatment on the primary nanofiltration concentrated water to obtain tertiary nanofiltration concentrated water and tertiary nanofiltration water; carrying out electrically driven membrane concentration treatment and evaporative crystallization treatment on the three-stage nanofiltration concentrated water to obtain an industrial-grade sodium sulfate product; and carrying out reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electric driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water production water, the secondary nanofiltration water production water and the tertiary nanofiltration water production water to obtain an industrial grade sodium chloride product. By removing pollutants such as organic matters and inorganic matters in the coking wastewater and separating and concentrating sodium chloride and sodium sulfate, zero discharge of the coking wastewater is realized.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a zero-discharge treatment method for coking wastewater.
Background
The coking wastewater has complex components, high organic matter content and high content of polycyclic aromatic hydrocarbon and macromolecular substances, and belongs to wastewater difficult to be biochemically treated. At present, domestic iron and steel united enterprises, coal coke united enterprises or independent coking enterprises for wet quenching generally biochemically treat coking wastewater to achieve the standards of recycling quenching coke and blast furnace slag flushing, and then realize the requirement of recycling, and the mode is the most extensive and low in cost, but has the problems of pollutant transfer, equipment corrosion and the like. Organic matters of pollutants such as difficultly-degraded volatile phenol, ammonia nitrogen, cyanogen and the like contained in the effluent are difficult to remove, and harm is caused to the environment. The coke dry quenching independent coking enterprises and part of steel and iron united enterprises can not recycle the coking wastewater by adopting the modes of wet quenching and the like, and the problem of difficult treatment of concentrated water exists.
Admission conditions (revised 2008) of coking industry indicate that advanced applicable technologies such as dry coke quenching and coking wastewater advanced treatment and recycling are encouraged to be adopted by coking production enterprises. The zero discharge of the coking wastewater is a circular economy system, the coking wastewater is recycled, the sewage is recycled, the total amount of industrial water can be reduced, the dilemma of serious shortage of water resources is relieved, the pollution discharge cost can be saved, and the environment is protected.
Disclosure of Invention
The invention aims to provide a zero-discharge treatment method for coking wastewater, which can effectively remove pollutants in the coking wastewater, obtain industrial sodium chloride salt and industrial sodium sulfate salt products and realize zero discharge of the coking wastewater.
In order to achieve the above object, the present invention provides a zero discharge treatment method for coking wastewater, which is used for treating coking wastewater after biochemical treatment, and comprises:
pretreating the coking wastewater, wherein the pretreatment comprises flocculation treatment, ultrafiltration treatment and softened water treatment;
carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration produced water and primary nanofiltration concentrated water;
carrying out secondary nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and tertiary nanofiltration treatment on the primary nanofiltration concentrated water to obtain tertiary nanofiltration concentrated water and tertiary nanofiltration water;
carrying out electrically driven membrane concentration treatment and evaporative crystallization treatment on the three-stage nanofiltration concentrated water to obtain an industrial-grade sodium sulfate product;
and carrying out reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electric driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water production water, the secondary nanofiltration water production water and the tertiary nanofiltration water production water to obtain an industrial grade sodium chloride product.
Optionally, the flocculation treatment is performed in a high-efficiency flocculation reactor, and a flocculating agent, a defluorinating agent and a coagulant aid are added into the high-efficiency flocculation reactor to perform flocculation treatment on the coking wastewater.
Optionally, the flocculant is a carbon-based active high-efficiency flocculant, and the defluorinating agent is an aluminum flocculation defluorinating agent.
Optionally, an immersed ultrafiltration membrane or a pressure ultrafiltration membrane is used for ultrafiltration treatment of the coking wastewater.
Optionally, weakly acidic cationic resin is used for softening the coking wastewater to remove calcium ions and magnesium ions in the coking wastewater, the weakly acidic cationic resin is regenerated through hydrochloric acid and sodium hydroxide, the generated regenerated waste liquid is softened by a double alkali method, and softened effluent is returned for efficient flocculation treatment.
Optionally, electrically driven membrane concentration treatment is performed by using a homogeneous electrically driven membrane.
Optionally, a multi-section reverse osmosis membrane and a sea water desalination reverse osmosis membrane are adopted to carry out reverse osmosis membrane concentration treatment on the first-stage nanofiltration water production, the second-stage nanofiltration water production and the third-stage nanofiltration water production.
Optionally, the tubular microfiltration treatment is performed in a tubular microfiltration circulation tank, and a fluorine removal agent and a silicon removal agent are added into the tubular microfiltration circulation tank to remove fluorine ions and silicon dioxide in the coking wastewater.
Optionally, a steam mechanical recompression technology or a multi-effect evaporation technology is adopted for carrying out evaporation crystallization treatment, so as to obtain an industrial-grade sodium sulfate product and an industrial-grade sodium chloride product.
Optionally, after the evaporation crystallization treatment is performed on the three-stage nanofiltration concentrated water by adopting a steam mechanical recompression technology or a multiple-effect evaporation technology, the generated sodium sulfate mother liquor is sent to a regeneration waste liquor pool, is uniformly mixed with the regeneration waste liquor and then is softened by adopting a double alkali method, and the softened effluent is returned to the high-efficiency flocculation treatment.
The invention provides a zero-discharge treatment method for coking wastewater, which is used for treating the coking wastewater after biochemical treatment and pretreating organic matters and F in the coking wastewater-And pollutants such as silicon dioxide, calcium ions, magnesium ions and the like are removed, so that stable operation of various subsequent treatment membranes and evaporative crystallization equipment is facilitated, sodium chloride and sodium sulfate in the coking wastewater are separated through primary nanofiltration, and industrial sodium chloride salt and industrial sodium sulfate salt products are obtained by respectively concentrating, evaporating and crystallizing in different modes, so that zero discharge of the coking wastewater is realized.
Drawings
FIG. 1 is a process diagram of a zero discharge treatment method for coking wastewater according to an embodiment of the present invention;
fig. 2 is a flow chart of a zero discharge treatment method for coking wastewater provided by the embodiment of the invention.
Detailed Description
The following describes in more detail embodiments of the present invention with reference to the schematic drawings. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
As shown in fig. 1 and fig. 2, the present embodiment provides a zero discharge treatment method for coking wastewater, which is used for treating coking wastewater after biochemical treatment, and includes:
step S1: pretreating the coking wastewater, wherein the pretreatment comprises flocculation treatment, ultrafiltration treatment and softened water treatment;
step S2: carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration produced water and primary nanofiltration concentrated water;
step S3: carrying out secondary nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and tertiary nanofiltration treatment on the primary nanofiltration concentrated water to obtain tertiary nanofiltration concentrated water and tertiary nanofiltration water;
step S4: carrying out electrically driven membrane concentration treatment and evaporative crystallization treatment on the three-stage nanofiltration concentrated water to obtain an industrial-grade sodium sulfate product;
step S5: and carrying out reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electric driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water production water, the secondary nanofiltration water production water and the tertiary nanofiltration water production water to obtain an industrial grade sodium chloride product.
Specifically, the coking wastewater zero-discharge treatment method provided by the embodiment is used for treating coking wastewater, and the water inlet indexes of the coking wastewater are as follows: PH is 7-8, COD is 250-300 mg/L, Cl-2000 mg/L-3000 mg/L,
is 800mg/L to 1500mg/L of Na+1100mg/L to 3000mg/L, F-42mg/L-57mg/L, total nitrogen 7 mg/L-28 mg/L, calcium ion 10 mg/L-32 mg/L, magnesium ion 1 mg/L-10 mg/L, TDS (total dissolved solids) 4700 mg/L-7000 mg/L, and suspended matter (SS) 10 mg/L-50 mg/L.
Firstly, step S1 is executed to perform pretreatment on the coking wastewater, wherein the pretreatment includes flocculation treatment, ultrafiltration treatment and softened water treatment. The method comprises the following specific steps:
flocculation treatment: and the flocculation treatment is carried out in a high-efficiency flocculation reactor, and a flocculating agent, a defluorinating agent and a coagulant aid are added into the high-efficiency flocculation reactor to flocculate the coking wastewater. Organic matter and F in the coking wastewater are treated by flocculation-Removing silicon dioxide and calcium ions, and after treatment, reducing COD of effluent to below 80mg/l, and F-The concentration is reduced to below 4 mg/l.
In this embodiment, the flocculating agent is the active high-efficient flocculating agent of charcoal base, relies on the developed pore structure of active high-efficient flocculating agent of charcoal base and huge specific surface area, can fully get rid of long-chain organic matter and benzene ring class organic matter in the coking wastewater, reduces COD content, reduces the influence that benzene ring class organic matter destroys the membrane surface (receive filter membrane, reverse osmosis membrane, electric drive membrane) active layer.
In this embodiment, the fluorine removing agent is an aluminum flocculation fluorine removing agent. Under the large-flux circulation reaction in the high-efficiency flocculation reactor, F-Can react with active aluminum ions in the coking wastewater to generate precipitates for convenient removal. F-The content of F is reduced from 42mg/l to 57mg/l to less than 4mg/l-Influence on subsequent electrically driven membrane electrode and vapor mechanical recompression (MVR) titanium material.
And (3) ultrafiltration treatment: and (2) carrying out ultrafiltration treatment on the coking wastewater by adopting an immersed ultrafiltration membrane (SUF) or a pressure ultrafiltration membrane, and further separating particulate matters, macromolecular organic matters, microorganisms and the like in the coking wastewater from fluid and dissolved components to ensure that suspended matters (SS) in effluent are less than 1 mg/L.
Water softening treatment: softening the coking wastewater by using weakly acidic cationic resin to remove calcium ions and magnesium ions in the coking wastewater, regenerating the weakly acidic cationic resin by using hydrochloric acid and sodium hydroxide, softening the generated regenerated waste liquid by using a double-alkali method, and returning softened water to efficient flocculation treatment. In the embodiment, the weakly acidic cation resin can remove calcium ions and magnesium ions in the wastewater, and after the wastewater is treated by the weakly acidic cation resin, the contents of the calcium ions and the magnesium ions in the effluent are both less than 1.0 mg/l; after the weakly acidic cation resin is operated for a period, the hydrochloric acid and sodium hydroxide are used for regeneration, and the generated regeneration waste liquid (the calcium ion concentration is 800-1500mg/l, the magnesium ion concentration is 100-400mg/l) is softened by a double-alkali method, so that the calcium ion concentration of the effluent is lower than 30mg/l, and the magnesium ion concentration is lower than 15 mg/l.
And then executing step S2, and carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration product water and primary nanofiltration concentrated water. Efficient separation of Cl by primary nanofiltration-And
the purity of sodium chloride and sodium sulfate is effectively guaranteed, the sodium sulfate evaporation crystallization device can continuously operate for a long time, and the amount of sodium sulfate mother liquor is reduced. In this example, the first stage nanofiltration produces water:
40mg/L to 100mg/L, and the content of calcium ions is<1mg/L, magnesium ion content of<1mg/L, COD content of 10 mg/L-30 mg/L, TDS of 5000 mg/L-7000 mg/L, and the following components in the first-stage nanofiltration concentrated water:
4000 mg/L-6000 mg/L, 4 mg/L-10 mg/L of calcium ion content, 4 mg/L-10 mg/L of magnesium ion content, 200 mg/L-280 mg/L of COD content and 11500 mg/L-14000 mg/L of TDS (total dissolved solids).
And then, step S3 is executed, and the first-stage nanofiltration concentrated water is subjected to second-stage nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and third-stage nanofiltration treatment to obtain third-stage nanofiltration concentrated water and third-stage nanofiltration water. The method comprises the following specific steps:
and (3) secondary nanofiltration treatment: is used for concentrating and lifting the first-stage nanofiltration concentrated water
Concentration, two-stage nanofiltration concentrated water
8000 mg/L-12000 mg/L TDS (total dissolved solid) 18000 mg/L-22000 mg/L. In the embodiment, the obtained secondary nanofiltration produced water is returned to the primary nanofiltration for retreatment, and the secondary nanofiltration concentrated water is sent to a secondary nanofiltration concentrated water tank.
Activated carbon adsorption treatment: after nanofiltration separation, the sodium sulfate side organic matters are enriched, the secondary nanofiltration concentrated water is adsorbed by active carbon, and the organic matters are chemically adsorbed to the surface of the carbon by the action of van der Waals force between the organic matters and the functional group oxygen on the surface of the carbon, so that the enriched organic matters can be effectively removed.
Tubular microfiltration treatment: the method is carried out in a tubular microfiltration circulating tank, and fluorine ions and silicon dioxide in the coking wastewater are removed by adding a fluorine removing agent and a silicon removing agent into the tubular microfiltration circulating tank. In the embodiment, under the action of tubular microfiltration large-flux circulation, the agent is fully contacted with fluorine and silicon pollutants in the coking wastewater, and then is precipitated in sludge through complexation, adsorption and other actions, so that the removal effect is achieved.
And (3) three-stage nanofiltration treatment: designing 2 sections of three-stage nanofiltration, wherein the pressure of a high-pressure pump is 2-4Mpa, concentrated water is concentrated by 2-4 times, and concentrated water is subjected to three-stage nanofiltration:
30000 mg/L-50000 mg/L, TDS (total dissolved solids) 50000 mg/L-75000 mg/L. In the embodiment, the obtained three-stage nanofiltration produced water is returned to the first-stage nanofiltration for retreatment, and the three-stage nanofiltration concentrated water is sent to an electric drive membrane for concentration.
And step S4 is executed, and the three-stage nanofiltration concentrated water is subjected to electric drive membrane concentration treatment and evaporation crystallization treatment to obtain an industrial-grade sodium sulfate product.
In the embodiment, a homogeneous phase electric driven membrane is adopted for carrying out electric driven membrane concentration treatment, and the concentrated water of the three-stage nanofiltration is concentrated by a sodium sulfate electric driven membrane and then is added into the concentrated water
60000 mg/L-80000 mg/L, TDS 110000 mg/L-150000 mg/L, F-Is composed of<4mg/l, silica<10 mg/l. After concentration by using nanofiltration and an electrically driven membrane, the concentration of sodium sulfate can be increased to 12-15%. In the general sodium sulfate concentration process in the market, due to the concentration of the membrane, the enrichment of pollutants is increased, and the membrane is easy to pollute and block. This application is through getting rid of various pollutants (COD, calcium ion, magnesium ion and fluorinion etc.), can make the stable long-time operation of membrane system to can promote sodium sulfate concentration to the design value. In the embodiment, the obtained electric drive membrane produced water is returned to the secondary nanofiltration concentrated water tank for retreatment, and the electric drive membrane concentrated water is sent to the evaporation crystallization device for treatment.
In this embodiment, an evaporation crystallization process is performed by using a vapor mechanical recompression (MVR) technology or a multiple-effect evaporation technology, so as to obtain an industrial-grade sodium sulfate product. And (3) concentrating, centrifuging and drying by adopting an MVR device to obtain the industrial-grade sodium sulfate with the purity of more than 95.0%. In order to ensure the purity of the sodium sulfate, a small amount of sodium sulfate mother liquor is periodically discharged from a sodium sulfate evaporation crystallization system, the generated sodium sulfate mother liquor is sent to a regeneration waste liquor pool, the generated sodium sulfate mother liquor is uniformly mixed with regeneration waste liquor and then softened by adopting a double-alkali method, softened effluent is returned to be subjected to efficient flocculation treatment, a cycle is formed, and the secondary treatment of the coking wastewater is realized. The industrial new water generated by evaporation and crystallization can be directly recycled.
And simultaneously executing the step S4, synchronously executing the step S5, and performing reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electrically-driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water product, the secondary nanofiltration water product and the tertiary nanofiltration water product to obtain an industrial sodium chloride product. The method comprises the following specific steps:
concentrating treatment by a reverse osmosis membrane: adopts a multi-section reverse osmosis membrane and seawaterDesalting reverse osmosis membrane (SWRO) and treating. In this example, the reverse osmosis membrane is designed in two stages, and after concentration, the reverse osmosis concentrated water:
300mg/L to 500mg/L of Cl-10000mg/L-15000mg/L, TDS 20000 mg/L-27000 mg/L. After SWRO treatment, in SWRO concentrated water:
800 mg/L-1200 mg/L of Cl-12000mg/L-16000mg/L, TDS 35000 mg/L-55000 mg/L. In the embodiment, the industrial fresh water generated by the reverse osmosis membrane concentration treatment can be directly recycled.
Tubular microfiltration treatment: and (4) adding a fluorine removing agent and a silicon removing agent into the tubular microfiltration circulating tank to remove fluorine ions and silicon dioxide in the coking wastewater, as in the step S4.
Electrically driven membrane concentration treatment: as in step S4, the electrically driven membrane concentration treatment is performed using a homogeneous electrically driven membrane. After being concentrated by a sodium chloride electrically driven membrane, the TDS in the concentrated water is 135000-160000 mg/L and Cl-80000mg/L to 120000 mg/L. And returning the obtained electric driving membrane produced water to a reverse osmosis membrane for retreatment, and sending the electric driving membrane concentrated water to an evaporation crystallization device for treatment.
And (3) evaporation crystallization treatment: directly feeding the sodium chloride electric-driven membrane concentrated solution into a sodium chloride evaporation crystallization, concentration, centrifugation and packaging system to obtain an industrial-grade sodium chloride product with the purity of more than 98.5 percent. In order to ensure the purity of the sodium chloride salt, a sodium chloride evaporation crystallization system discharges a small amount of mother liquor periodically, the concentrated solution is discharged to the waste water regeneration waste liquid, and an evaporation crystallization device adopts an MVR (mechanical vapor recompression) technology or a multi-effect evaporation technology, so that the energy consumption is reduced to the maximum extent.
In this embodiment, the corresponding process units are arranged to effectively remove the organic matters, fluorine ions, calcium and magnesium ions, and silicon in the coking wastewater, and zero emission can be stably realized. In addition, after membrane treatment, separation and purification, the produced industrial fresh water has high water quality.
To sum up, the embodiment of the present invention provides a zero discharge treatment method for coking wastewater, which is used for treating coking wastewater after biochemical treatment, and includes: pretreating the coking wastewater, wherein the pretreatment comprises flocculation treatment, ultrafiltration treatment and softened water treatment; carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration produced water and primary nanofiltration concentrated water; carrying out secondary nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and tertiary nanofiltration treatment on the primary nanofiltration concentrated water to obtain tertiary nanofiltration concentrated water and tertiary nanofiltration water; carrying out electrically driven membrane concentration treatment and evaporative crystallization treatment on the three-stage nanofiltration concentrated water to obtain an industrial-grade sodium sulfate product; and carrying out reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electric driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water production water, the secondary nanofiltration water production water and the tertiary nanofiltration water production water to obtain an industrial grade sodium chloride product. Organic matters, fluoride ions, silicon dioxide, calcium ions and magnesium ions in the coking wastewater are removed, sodium chloride and sodium sulfate in the coking wastewater are separated and concentrated, and industrial sodium chloride salt and industrial sodium sulfate salt products are obtained through evaporation and crystallization, so that zero discharge of the coking wastewater is realized.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A zero discharge treatment method of coking wastewater is used for treating the coking wastewater after biochemical treatment, and is characterized by comprising the following steps:
pretreating the coking wastewater, wherein the pretreatment comprises flocculation treatment, ultrafiltration treatment and softened water treatment;
carrying out primary nanofiltration treatment on the pretreated coking wastewater to obtain primary nanofiltration produced water and primary nanofiltration concentrated water;
carrying out secondary nanofiltration treatment, activated carbon adsorption treatment, tubular microfiltration treatment and tertiary nanofiltration treatment on the primary nanofiltration concentrated water to obtain tertiary nanofiltration concentrated water and tertiary nanofiltration water;
carrying out electrically driven membrane concentration treatment and evaporative crystallization treatment on the three-stage nanofiltration concentrated water to obtain an industrial-grade sodium sulfate product;
and carrying out reverse osmosis membrane concentration treatment, tubular microfiltration treatment, electric driven membrane concentration treatment and evaporative crystallization treatment on the primary nanofiltration water production water, the secondary nanofiltration water production water and the tertiary nanofiltration water production water to obtain an industrial grade sodium chloride product.
2. The coking wastewater zero-discharge treatment method of claim 1, characterized in that the flocculation treatment is carried out in a high-efficiency flocculation reactor, and the coking wastewater is flocculated by adding a flocculating agent, a defluorinating agent and a coagulant aid into the high-efficiency flocculation reactor.
3. The coking wastewater zero-discharge treatment method according to claim 2, characterized in that the flocculant is a carbon-based active high-efficiency flocculant, and the defluorinating agent is an aluminum-based flocculation defluorinating agent.
4. The coking wastewater zero-discharge treatment method according to claim 1, characterized in that the coking wastewater is subjected to ultrafiltration treatment by using an immersion type ultrafiltration membrane or a pressure type ultrafiltration membrane.
5. The coking wastewater zero-discharge treatment method as claimed in claim 1, characterized in that weakly acidic cationic resin is adopted to carry out softened water treatment on the coking wastewater so as to remove calcium ions and magnesium ions in the coking wastewater, the weakly acidic cationic resin is regenerated by hydrochloric acid and sodium hydroxide, the generated regenerated waste liquid is softened by a double alkali method, and softened effluent is returned for efficient flocculation treatment.
6. The coking wastewater zero-discharge treatment method of claim 1, characterized in that electrically driven membrane concentration treatment is carried out by using a homogeneous electrically driven membrane.
7. The coking wastewater zero-discharge treatment method according to claim 1, characterized in that the reverse osmosis membrane concentration treatment is carried out on the primary nanofiltration water production, the secondary nanofiltration water production and the tertiary nanofiltration water production by using a multi-stage reverse osmosis membrane and a seawater desalination reverse osmosis membrane.
8. The coking wastewater zero-emission treatment method of claim 1, characterized in that the tubular microfiltration treatment is carried out in a tubular microfiltration circulating tank, and fluorine ions and silicon dioxide in the coking wastewater are removed by adding a fluorine removing agent and a silicon removing agent into the tubular microfiltration circulating tank.
9. The coking wastewater zero-emission treatment method of claim 1, characterized in that the steam mechanical recompression technology or the multi-effect evaporation technology is adopted for evaporation and crystallization treatment to obtain industrial-grade sodium sulfate products and industrial-grade sodium chloride products.
10. The coking wastewater zero-discharge treatment method of claim 9, characterized in that after the evaporation crystallization treatment is carried out on the three-stage nanofiltration concentrated water by adopting a steam mechanical recompression technology or a multi-effect evaporation technology, the generated sodium sulfate mother liquor is sent to a regeneration waste liquor pool, is uniformly mixed with the regeneration waste liquor, is softened by adopting a double alkali method, and the softened effluent is returned to the high-efficiency flocculation treatment.
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